CN103154320A - Anti-reflective articles with nanosilica-based coatings - Google Patents

Anti-reflective articles with nanosilica-based coatings Download PDF

Info

Publication number
CN103154320A
CN103154320A CN2011800483995A CN201180048399A CN103154320A CN 103154320 A CN103154320 A CN 103154320A CN 2011800483995 A CN2011800483995 A CN 2011800483995A CN 201180048399 A CN201180048399 A CN 201180048399A CN 103154320 A CN103154320 A CN 103154320A
Authority
CN
China
Prior art keywords
film
layer
goods
nanometers
coating
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN2011800483995A
Other languages
Chinese (zh)
Other versions
CN103154320B (en
Inventor
T·J·赫布林克
景乃勇
J·A·赖德尔
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
3M Innovative Properties Co
Original Assignee
3M Innovative Properties Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 3M Innovative Properties Co filed Critical 3M Innovative Properties Co
Publication of CN103154320A publication Critical patent/CN103154320A/en
Application granted granted Critical
Publication of CN103154320B publication Critical patent/CN103154320B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
    • H01L31/0236—Special surface textures
    • H01L31/02366—Special surface textures of the substrate or of a layer on the substrate, e.g. textured ITO/glass substrate or superstrate, textured polymer layer on glass substrate
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K31/00—Medicinal preparations containing organic active ingredients
    • A61K31/70—Carbohydrates; Sugars; Derivatives thereof
    • A61K31/7088—Compounds having three or more nucleosides or nucleotides
    • A61K31/7105—Natural ribonucleic acids, i.e. containing only riboses attached to adenine, guanine, cytosine or uracil and having 3'-5' phosphodiester links
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
    • C12N15/00—Mutation or genetic engineering; DNA or RNA concerning genetic engineering, vectors, e.g. plasmids, or their isolation, preparation or purification; Use of hosts therefor
    • C12N15/09—Recombinant DNA-technology
    • C12N15/11—DNA or RNA fragments; Modified forms thereof; Non-coding nucleic acids having a biological activity
    • C12N15/113—Non-coding nucleic acids modulating the expression of genes, e.g. antisense oligonucleotides; Antisense DNA or RNA; Triplex- forming oligonucleotides; Catalytic nucleic acids, e.g. ribozymes; Nucleic acids used in co-suppression or gene silencing
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
    • C12N15/00—Mutation or genetic engineering; DNA or RNA concerning genetic engineering, vectors, e.g. plasmids, or their isolation, preparation or purification; Use of hosts therefor
    • C12N15/09—Recombinant DNA-technology
    • C12N15/63—Introduction of foreign genetic material using vectors; Vectors; Use of hosts therefor; Regulation of expression
    • C12N15/79—Vectors or expression systems specially adapted for eukaryotic hosts
    • C12N15/85—Vectors or expression systems specially adapted for eukaryotic hosts for animal cells
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C24/00—Coating starting from inorganic powder
    • C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings
    • G02B1/113—Anti-reflection coatings using inorganic layer materials only
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/04—Prisms
    • G02B5/045—Prism arrays
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
    • H01L31/0216—Coatings
    • H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
    • H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
    • H01L31/02168—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells the coatings being antireflective or having enhancing optical properties for the solar cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
    • H01L31/0232—Optical elements or arrangements associated with the device
    • H01L31/02327—Optical elements or arrangements associated with the device the optical elements being integrated or being directly associated to the device, e.g. back reflectors
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
    • C12N2310/00—Structure or type of the nucleic acid
    • C12N2310/10—Type of nucleic acid
    • C12N2310/14—Type of nucleic acid interfering N.A.
    • C12N2310/141—MicroRNAs, miRNAs
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B2207/00—Coding scheme for general features or characteristics of optical elements and systems of subclass G02B, but not including elements and systems which would be classified in G02B6/00 and subgroups
    • G02B2207/107—Porous materials, e.g. for reducing the refractive index
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/02—Diffusing elements; Afocal elements
    • G02B5/0205—Diffusing elements; Afocal elements characterised by the diffusing properties
    • G02B5/021—Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place at the element's surface, e.g. by means of surface roughening or microprismatic structures
    • G02B5/0231—Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place at the element's surface, e.g. by means of surface roughening or microprismatic structures the surface having microprismatic or micropyramidal shape
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/02—Diffusing elements; Afocal elements
    • G02B5/0273—Diffusing elements; Afocal elements characterized by the use
    • G02B5/0294—Diffusing elements; Afocal elements characterized by the use adapted to provide an additional optical effect, e.g. anti-reflection or filter
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24355—Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]
    • Y10T428/24372—Particulate matter
    • Y10T428/24421—Silicon containing

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Organic Chemistry (AREA)
  • Genetics & Genomics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Materials Engineering (AREA)
  • Optics & Photonics (AREA)
  • Biomedical Technology (AREA)
  • Power Engineering (AREA)
  • Electromagnetism (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Computer Hardware Design (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Zoology (AREA)
  • Molecular Biology (AREA)
  • Bioinformatics & Cheminformatics (AREA)
  • Biotechnology (AREA)
  • General Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Nanotechnology (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Sustainable Development (AREA)
  • Microbiology (AREA)
  • Plant Pathology (AREA)
  • Biophysics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Composite Materials (AREA)
  • Sustainable Energy (AREA)
  • Pharmacology & Pharmacy (AREA)
  • Medicinal Chemistry (AREA)
  • Epidemiology (AREA)
  • Animal Behavior & Ethology (AREA)

Abstract

Article comprising a transparent substrate having an anti-reflective, structured surface and a coating comprising a porous network of silica nanoparticles thereon, wherein the silica nanoparticles are bonded to adjacent silica nanoparticles.

Description

Antireflective article with the silica-based coating of nanometer titanium dioxide
Background technology
Textured surface has been used in multiple application to obtain optics beneficial effect, surface energy modification, the control of tackiness agent viscosity and drag reduction.For example, the lip-deep prism structure of photovoltaic panel can reduce reflection and more light is guided to silion cell, thus increasing power output.When being applied to automobile, ship etc. or being applied to wind turbine or turbine blade, similarly prism structure will promote from the teeth outwards mobile of fluid, make resistance reduce.
Because the cost based on the conventional power generation usage of the combustion of fossil fuels power station of oil and coal (for example, based on) raises and the investment that reduces in the unconventional power supply of needs of the greenhouse gases of following increases.For example, USDOE has been carried out great amount of investment in the research and development of solar electrical energy generation (for example, the hot water based on sun power generates and generating).A kind of so unconventional energy source is with photovoltaic cell, solar energy to be converted into electricity.Solar energy also has been used to directly or indirectly, and heating water uses for dwelling house and business.The degree of concern that improves therewith one, thus the amount that this type of unconventional heliotechnics can absorb the efficient of luminous energy and increase operational sun power need to be improved.Thereby, be desirably in and place anti-reflecting surface between energy conversion and the sun in order to reduce surface reflection and increase transmission.A FAQs following anti-reflecting surface is to pollute and therefore reduce or prevent on the antagonistic reflex surface needs of the coating that dirt, sand, wet goods gather.
Summary of the invention
In one aspect, the invention describes a kind of goods, described goods comprise transparent substrate (for example film) with anti-reflection structure surface and the sinter fuse coating of the porous network that comprises Nano particles of silicon dioxide (being generally three-dimensional network) on it, and wherein said Nano particles of silicon dioxide is bonded to adjacent Nano particles of silicon dioxide.Fig. 2 shows the Nano particles of silicon dioxide 2 that not yet is sintered.Fig. 3 shows the Nano particles of silicon dioxide 3 of sour sintering.
On the other hand, the invention provides a kind of method for preparing goods as herein described, described method comprises:
Apply on the anti-reflection structure surface of transparent substrate comprise Nano particles of silicon dioxide coating composition so that coating to be provided, the pH of wherein said coating composition is lower than 3; With
Make Nano particles of silicon dioxide acid sintering, so that goods to be provided.
On the other hand, the invention provides a kind of method for preparing goods as herein described, described method comprises:
Apply on the anti-reflection structure surface of transparent substrate comprise Nano particles of silicon dioxide coating composition so that coating to be provided; With
Heat described coating so that goods to be provided.
On the other hand, the invention provides a kind of method for preparing goods as herein described, described method comprises:
Apply on the anti-reflection structure surface of transparent substrate comprise the core-shell silica nanoparticle coating composition so that coating to be provided, wherein each core-shell particles comprises polymer core, the shell that described polymer core is disposed in the atresia preparing spherical SiO 2 particles on polymer core holds, and the volume average particle size of wherein said atresia preparing spherical SiO 2 particles is not more than 60 nanometers (in certain embodiments, be not more than 50 nanometers, 40 nanometers, 30 nanometers, 20 nanometers or not even greater than 10 nanometers); With
Heat described coating so that goods to be provided.
In present patent application:
" antireflection " means to reflect the surface lower than 4% under normal angle;
" sintering " means the bonding of the adjacently situated surfaces of particle;
" textured surface " means any non-planar surfaces; With
" porous network of Nano particles of silicon dioxide " means to form when nanoparticle the existence in space between the Nano particles of silicon dioxide that is producing when continuous coated.Preferably, when drying, the porosity of network is 25 volume % to 45 volume %, more preferably is 30 volume % to 40 volume %.In certain embodiments, porosity can be higher.Porosity can be pressed for example W.L.Bragg from the specific refractory power of coating, A.B.Pippard, Acta Crystallographica (" crystallization journal "), volume 6 (the 6th volume), the program of announcing in page 865 (the 865th page) (1953) is calculated, and the disclosure of the document is incorporated herein by reference.Any exemplary three dimensional porous network of Nano particles of silicon dioxide has been shown in Fig. 1.
In addition, as used herein, the base material that term " transparent " means to allow the light transmission of required bandwidth to pass through.As used in this article in this term, that base material can also not be considered to clarify and be still transparent.That is to say, as used in this article in this term, base material can be considered to muddy and be still transparent.Expectation is passed through according to the light transmission of transparent substrate permission 85%, 91%, 92%, 93%, 94%, 95%, 96%, 97% or 98% of the present invention at least.The transparent electromagnetic wavelength of expectation comprise visual range (namely approximately 400nm to about 2500nm, in certain embodiments, preferred approximately 400nm is to about 1150nm) and/or near infrared (IR) scope (namely approximately 700nm to about 2500nm), but other transparent electromagnetic wavelengths are also available.
The purposes of goods as herein described comprises luminous energy absorption unit (for example photovoltaic devices) and solar heat heating unit.
Description of drawings
Fig. 1 is the scanning electron photomicrograph of the exemplary three dimensional porous network of Nano particles of silicon dioxide.
Fig. 2 is the scanning electron photomicrograph on porous nanometer structure surface before sintering.
Fig. 3 is the scanning electron photomicrograph through the porous nanometer structure surface of sintering.
Fig. 4 is the illustrative diagram of Nano particles of silicon dioxide coating on the anti-reflecting surface structure on the stable base material of UV.
Fig. 5 is the illustrative diagram with Nano particles of silicon dioxide coating on the anti-reflecting surface structure of crosslinked gradient.
Fig. 6 is the illustrative diagram that has Nano particles of silicon dioxide coating on the anti-reflecting surface structure of prism on the stable base material of UV.
Fig. 7 is the illustrative diagram of Nano particles of silicon dioxide coating on the anti-reflecting surface structure on the stable base material of UV.
Fig. 8 is the camera digital picture of the cross section of the exemplary acids fused silica nanoparticle that is coated with on the anti-reflecting surface structure.
Fig. 9 is the illustrative diagram of the geometrical shape of anti-reflecting surface structure.
Figure 10 is the cross section with the exemplary flexible anti-reflecting surface structure on blocking layer.
Figure 11 is the cross section of exemplary flexible photovoltaic module.
Embodiment
The exemplary transparent substrate on anti-reflection structure surface comprises polymer materials (for example, film and sheet material) and glass.Typical polymer materials comprises acrylate, polyester, polycarbonate, cyclic olefine copolymer, organosilicon and fluoropolymer.Polymeric film comprises multi-layer optical film.Usually, multi-layer optical film comprises at least 100 layers (usually in 100 to 2000 layer scopes altogether or more).
other examples of polymer materials comprise that polyester (for example, polyethylene terephthalate, polybutylene terephthalate), cyclic olefine copolymer (COC), fluoropolymer (for example, ethylene-tetrafluoroethylene, poly(vinylidene fluoride), THV), polycarbonate, allyl diglycol carbonates, polyacrylic ester such as polymethylmethacrylate, polystyrene, polysulfones, polyethersulfone, the epoxy homopolymer, epoxy addition polymer with poly-diamines, poly-two mercaptan, polyethylene and ethylene copolymers, fluorinated surface, cellulose ester (for example, acetic ester and butyric ester).In certain embodiments, base material is flexible and by polyester (for example, polyethylene terephthalate (PET)), (for example, PP (polypropylene), PE (polyethylene) and PVC (polyvinyl chloride) make for cyclic olefine copolymer (COC) and polyolefine.
The masking technique of available routine is shaped to film with substrate, for example base resin film extrusion and the optional extruded film that makes is carried out single shaft or diaxial orientation.Suitable commercial membrane comprises can for example derive from the Connecticut State watt woods Ford's (the Rowland Industries of Rowland industrial with trade(brand)name " SOLATUF ", Wallingford, CT) polymethylmethacrylate (PMMA) film and can trade(brand)name " OPTICAL LIGHTING FILM FILM 2301 " derive from (the 3M Company of 3M company in Sao Paulo, the Minnesota State, St.Paul, MN) polycarbonate (PC) film.
Other available aggretion type base materials comprise that UV (is UV-light, its wavelength is less than 400nm) mirror be for example it with 1/4th multi-layer optical film of the light wavelength that reflects by the thickness of the alternating layer of the stable polyethylene terephthalate of UV (PET) and (methyl) methyl acrylate-ethyl acrylate copolymer (CoPMMA) structure.This UV speculum has polymer layer alternately, and thickness is at reflection UV light and by in the scope of visible light.Be found in the patent application of the common pending trial with United States serial 61/262,417 of submitting on November 18th, 2009 about other details of these films, the disclosure of this patent application is incorporated herein by reference.
Other available aggretion type base materials comprise the IR mirror, for example known in the art those, comprise by the thickness of the alternating layer of the stable polyethylene terephthalate of UV (PET) and Eudragit NE30D (CoPMMA) structure being its multi-layer optical film of 1/4th with the light wavelength of reflection.This IR speculum has polymer layer alternately, and thickness is at reflection IR light and by in the scope of visible light.Be found in about other details of these films and have U.S. Patent number 4,229,066 (people such as Rancourt), 5,233,465 (people such as Wheatley), 5,449,413 (people such as Beauchamp), 6,049,419 (people such as Wheatley), 7,019,905 (Weber), 7,141,297 (people such as Condo) and 7, the patent application of the common pending trial of 215,473 (Fleming), the disclosure of these patent applications is incorporated herein by reference.
in certain embodiments, the UV stabilized base material comprises multi-layer optical film, described multi-layer optical film comprises: more than first at least the first and second optical layers, and the 3rd optical layers, described more than first at least the first and second optical layers have major surfaces and jointly are reflected in the wavelength region of 300 nanometer to 400 nanometers at least 30 nanometers at least (in certain embodiments, at least 35 nanometers, 40 nanometers, 45 nanometers, 50 nanometers, 55 nanometers, 60 nanometers, 65 nanometers, 70 nanometers, 75 nanometers, 80 nanometers, 85 nanometers, 90 nanometers, 95 nanometers, or at least 100 nanometers even) wavelength region above at least 50% (in certain embodiments, at least 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 96%, 97%, or even at least 98%) incident UV light, described the 3rd optical layers has first and second common relative the first and second major surfacess and jointly be absorbed in the wavelength region of 300 nanometer to 400 nanometers at least 30 nanometers at least (in certain embodiments, at least 35 nanometers, 40 nanometers, 45 nanometers, 50 nanometers, 55 nanometers, 60 nanometers, 65 nanometers, 70 nanometers, 75 nanometers, 80 nanometers, 85 nanometers, 90 nanometers, 95 nanometers, or at least 100 nanometers even) wavelength region above at least 50% (in certain embodiments, at least 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, or even at least 95%) incident UV light, the major surfaces of wherein said a plurality of the first and second optical layers is near (namely within 1mm, in certain embodiments, be no more than 0.75mm, 0.5mm, 0.4mm, 0.3mm, 0.25mm, 0.2mm, 0.15mm, 0.1mm, or even within 0.05mm, in certain embodiments, contact) the first major surfaces of described the 3rd optical layers, and wherein there are more than second the first and second optical layers, described more than second the first and second optical layers have major surfaces, and jointly be reflected at least 30 nanometers (at least 35 nanometers in certain embodiments, in the wavelength region of at least 300 nanometer to 400 nanometers, 40 nanometers, 45 nanometers, 50 nanometers, 55 nanometers, 60 nanometers, 65 nanometers, 70 nanometers, 75 nanometers, 80 nanometers, 85 nanometers, 90 nanometers, 95 nanometers, or at least 100 nanometers even) wavelength region above at least 50% (in certain embodiments, at least 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 96%, 97%, or even at least 98%) incident UV light, described more than second the first and second optical layers are near (namely within 1mm, in certain embodiments, being no more than 0.75mm, 0.5mm, 0.4mm, 0.3mm, 0.25mm, 0.2mm, 0.15mm, 0.1mm, or even within 0.05mm, in certain embodiments, contact) the second major surfaces of described the 3rd optical layers.Randomly, first and/or the second layer at least some (in certain embodiments, first and/or at least 50 quantity % of the second layer, in certain embodiments, first or the second layer at least one whole) comprise the UV absorption agent.
Exemplary UV stabilized base material can be by coextrusion UV stable top layer (for example, PMMA (polymethylmethacrylate)/UVA (uv-absorbing agent), PMMA (polymethylmethacrylate)/PVDF (poly(vinylidene fluoride))/UVA (uv-absorbing agent)) Yu to the more unsettled polymkeric substance of UV (for example, polycarbonate and polyethylene terephthalate) form.Perhaps, can be to closing layer by layer or adhere to the stable top layer of UV to UV is more unsettled.Can change the thickness of the stable relative sandwich layer in top layer of UV with the physical properties of Properties of Optimization such as UV stability, ductility, toughness, hardness and other expectations.
in certain embodiments, multi-layer optical film comprises a plurality of at least the first and second optical layers, the 3rd optical layers and the 4th optical layers, described a plurality of at least the first and second optical layers have the first and second relative major surfacess, and jointly be reflected in the wavelength region of 300 nanometer to 400 nanometers at least 30 nanometers at least (in certain embodiments, at least 35 nanometers, 40 nanometers, 45 nanometers, 50 nanometers, 55 nanometers, 60 nanometers, 65 nanometers, 70 nanometers, 75 nanometers, 80 nanometers, 85 nanometers, 90 nanometers, 95 nanometers, or at least 100 nanometers even) wavelength region above at least 50% (in certain embodiments, at least 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 96%, 97%, or even at least 98%) incident UV light, described the 3rd optical layers has major surfaces, and be absorbed in the wavelength region of 300 nanometer to 400 nanometers at least 30 nanometers at least (in certain embodiments, at least 35 nanometers, 40 nanometers, 45 nanometers, 50 nanometers, 55 nanometers, 60 nanometers, 65 nanometers, 70 nanometers, 75 nanometers, 80 nanometers, 85 nanometers, 90 nanometers, 95 nanometers, or at least 100 nanometers even) wavelength region above at least 50% (in certain embodiments, at least 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, or even at least 95%) incident UV light, described the 3rd optical layers is near (namely within 1mm, in certain embodiments, be no more than 0.75mm, 0.5mm, 0.4mm, 0.3mm, 0.25mm, 0.2mm, 0.15mm, 0.1mm, or even within 0.05mm, in certain embodiments, contact) the first major surfaces of described a plurality of at least the first and second optical layers, described the 4th optical layers is absorbed in the wavelength region of 300 nanometer to 400 nanometers at least 30 nanometers at least (in certain embodiments, at least 35 nanometers, 40 nanometers, 45 nanometers, 50 nanometers, 55 nanometers, 60 nanometers, 65 nanometers, 70 nanometers, 75 nanometers, 80 nanometers, 85 nanometers, 90 nanometers, 95 nanometers, or at least 100 nanometers even) wavelength region above at least 50% (in certain embodiments, at least 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, or even at least 95%) incident UV light, described the 4th optical layers is near (namely within 1mm, in certain embodiments, be no more than 0.75mm, 0.5mm, 0.4mm, 0.3mm, 0.25mm, 0.2mm, 0.15mm, 0.1mm, or even within 0.05mm, in certain embodiments, contact) the second major surfaces of described a plurality of at least the first and second optical layers.Randomly, first and/or the second layer at least some (in certain embodiments, first and/or at least 50 quantity % of the second layer, in certain embodiments, first or the second layer at least one whole) comprise the UV absorption agent.
In certain embodiments, the refractive index difference of first and second layers that replaces of multi-layer optical film is at least 0.04 (in certain embodiments, at least 0.05,0.06,0.07,0.08,0.09,0.1,0.125,0.15,0.175,0.2,0.225,0.25,0.275 or even at least 0.3).In certain embodiments, described the first optical layers is birefringent and comprises birefringent polymer.In certain embodiments, at least one in first, second or the 3rd (if exist) optical layers be in fluoropolymer, organosilicon polymer, urethane polymer or acrylic ester polymer (blend that comprises them) at least one and preferably UV is stable.
Exemplary materials for the preparation of the optical layers (for example, the first and second optical layers) that reflects comprises polymkeric substance (for example, polyester comprises copolyesters and modified copolyester).In this article, term " polymer " " will be interpreted as and comprise homopolymer and multipolymer, and can by for example coetrusion or by the reaction that comprises transesterification reaction form can miscible blend polymkeric substance or multipolymer.Term " polymer " " and " multipolymer " comprise random copolymers and segmented copolymer.Be applicable to generally include dicarboxylic ester subunit and glycol subunit according to the polyester in some exemplary multi-layer optical films of disclosure structure, and can generate by the reaction of carboxylic acid ester monomer molecule and glycol monomer molecule.Each dicarboxylic ester monomer molecule has two or more carboxylic acid functionals or ester functional group, and each glycol monomer molecule has two or more hydroxy functional groups.The dicarboxylic ester monomer molecule is identical two or more dissimilar molecules that maybe may exist all.Glycol monomer molecule is also like this.Term " polyester " also comprises the polycarbonate derived from the reaction of glycol monomer molecule and carbonic ether.
The example of dicarboxylic acid monomer's molecule that is applicable to form the carboxylicesters subunit of polyester layer comprises: 2,6-naphthalene dicarboxylic acids and isomer thereof; Terephthalic acid; M-phthalic acid; Phthalic acid; Nonane diacid; Hexanodioic acid; Sebacic acid; Norbornene dicarboxylic acids; The double-octane dicarboxylic acid; Isosorbide-5-Nitrae-cyclohexane dicarboxylic acid and isomer thereof; Tert-butyl isophthalic acid, trimellitic acid, sodiosulfoisophthalic acid; 4,4 '-diphenyl dicarboxylic acid and isomer thereof; And these sour lower alkyl esters, for example methyl or ethyl ester.Term " low alkyl group " in this article refers to C 1-C 10The alkyl of straight or branched.
The example of glycol monomer molecule that is applicable to form the glycol subunit of polyester layer comprises: ethylene glycol; Propylene glycol, BDO and isomer thereof; 1,6-hexylene glycol; Neopentyl glycol; The polyoxyethylene glycol glycol ether; Three ring decanediols; 1,4 cyclohexane dimethanol and isomer thereof; The camphane glycol falls; Two ring ethohexadiols; TriMethylolPropane(TMP); Tetramethylolmethane; Isosorbide-5-Nitrae-xylyl alcohol and isomer thereof; Dihydroxyphenyl propane; 1,8-dihydroxybiphenyl and isomer thereof; And two (2-hydroxyl-oxethyl) benzene of 1,3-.
Another the exemplary birefringent polymer that can be used for the reflecting layer is polyethylene terephthalate (PET), and it can for example prepare by the reaction to benzene dicarboxylic acid and ethylene glycol.When polarization plane is parallel to draw direction, its to the specific refractory power of the polarized incident light of 550nm wavelength from approximately 1.57 increasing to up to approximately 1.69.Increasing molecular orientation increases the double refraction of PET.Molecular orientation can be by keeping other stretching conditions fixedly to increase material extending to larger stretch ratio.The multipolymer of PET (CoPET), for example U.S. Patent number 6,744,561 (people such as Condo) and U.S. Patent numbers 6, those that describe in 449,093 people such as () Hebrink, particularly useful, because the ability of its lesser temps (being usually less than 250 ℃) processing makes it with more compatible to the coextrusion of more unsettled the second polymkeric substance of heat, the disclosure of described patent is incorporated herein by reference.Other semicrystalline polyesters that are suitable as birefringent polymer comprise polybutylene terephthalate (PBT), polyethylene terephthalate (PET) and their multipolymer, for example U.S. Patent No. 6,449, those that describe in 093B2 people such as () Hebrink or U.S. Patent Publication numbers 20060084780 people such as () Hebrink, the disclosure of described patent is incorporated herein by reference.Another kind of available birefringent polymer is syndiotactic polystyrene (sPS).
In addition, for example, second (layer) polymkeric substance of multi-layer optical film can be by the second-order transition temperature of second-order transition temperature and the first layer the compatible and specific refractory power multiple polymers that is similar to the isotropic refractive index of birefringent polymer make.The example that is applicable to other polymkeric substance of blooming (particularly the second polymkeric substance) comprises vinyl polymer and the multipolymer that is made by the monomer such as vinyl naphthalene, vinylbenzene, maleic anhydride, acrylate and methacrylic ester.The example of this base polymer comprises polyacrylic ester, polymethacrylate (for example, gathering (methyl methacrylate) (PMMA)) and isotaxy or syndiotactic polystyrene.Other polymkeric substance comprise polycondensate, for example polysulfones, polymeric amide, urethane, polyamic acid and polyimide.In addition, the second polymkeric substance can be formed by the homopolymer of polyester, polycarbonate, fluoropolymer and poly-(dimethyl siloxane) and multipolymer and their blend.
The 3rd (UV absorption) optical layers (if existence) and the 4th (UV absorption) layer (if existence) comprise polymkeric substance and UV absorption agent, and preferably serve as the UV protective layer.Usually, described polymkeric substance is thermoplastic polymer.the example of suitable polymkeric substance comprises that polyester (for example, polyethylene terephthalate), fluoropolymer, acrylic resin (for example, polymethylmethacrylate), organosilicon polymer (for example, the thermoplastic silicone polymkeric substance), styrenic, polyolefine, olefin copolymer (advanced (the Topas Advanced Polymers of Polymer Company of Topas that for example can " TOPAS COC " derives from Florence, the Kentucky State, Florence, KY) ethene and the multipolymer of norbornylene), Organosiliconcopolymere, fluoropolymer and their combination are (for example, the blend of polymethylmethacrylate and poly(vinylidene fluoride)).
Be used for optical layers, draw together the homopolymer of polymethylmethacrylate (PMMA) especially for other illustrative polymers of the second layer, as can trade(brand)name " CP71 " and " CP80 " derive from Ineos Acrylics (the Ineos Acrylics of company of Wilmington, the Delaware State, Inc., Wilmington, DE) those, and second-order transition temperature is lower than the polyethyl methacrylate (PEMA) of PMMA.Other available polymkeric substance comprise the multipolymer (CoPMMA) of PMMA, the CoPMMA that is for example made by ethyl propenoate (EA) monomer of methyl methacrylate (MMA) monomer of 75 % by weight and 25 % by weight (can trade(brand)name " PERSPEX CP63 " derive from Ineos acrylic (the Ineos Acrylics of company, Inc.) or can trade(brand)name " ATOGLAS 510 " derive from (Arkema of Arkema of philadelphia, pa, Philadelphia, PA)); The CoPMMA that is formed by MMA comonomer unit and n-BMA (nBMA) comonomer unit; Or PMMA and poly-(vinylidene fluoride) blend (PVDF).
Be used for optical layers, comprise polyolefin copolymer in particular for other suitable polymkeric substance of the second layer, Tao Shi elastomerics (the Dow Elastomers of company that for example can trade(brand)name " ENGAGE 8200 " derives from available, Midland, MI) ethylene-octene copolymer (PE-PO); The propylene-ethylene copolymers (PPPE) that can trade(brand)name " Z9470 " derives from the petro-chemical corporation of Atofina (Atofina Petrochemicals, Inc., Houston, TX) of Houston, Texas; And the multipolymer of atactic polypropylene(APP) (aPP) and isotactic polyprophlene (iPP).Multi-layer optical film also can for example comprise functionalised polyolefin in the second layer, as maleic anhydride grafted linear low density polyethylene (LLDPE-g-MA), (the E.I.duPont de Nemours Co. of E.I.Du Pont Company that for example can trade(brand)name " BYNEL 4105 " derives from Wilmington, the Delaware State, Inc., Wilmington, DE).
comprise PMMA for the 3rd layer of the alternating layer with at least a birefringent polymer and/or the preferred polymeric compositions of the second layer, CoPMMA, poly-(dimethyl siloxane oxamide) basic chain segment copolymer (SPOX), fluoropolymer (comprises such as the homopolymer of PVDF with such as derived from tetrafluoroethylene, the multipolymer of those of R 1216 and vinylidene fluoride (THV)), the blend of PVDF/PMMA, acrylate copolymer, vinylbenzene, styrol copolymer, Organosiliconcopolymere, polycarbonate, Copolycarbonate, polycarbonate Alloys, the blend of polycarbonate and Zelan 338 and cyclic olefine copolymer.
For the preparation of the optical layers that reflects UV light (for example, the first and second optical layers) preferred material combination comprises that PMMA (for example, the first layer)/THV (for example, the second layer), PC (polycarbonate) (for example, the first layer)/PMMA (for example, the second layer), PET are (for example, the first layer)/CoPMMA (for example, the second layer) and PET (for example, the first layer)/PVDF/PMMA blend (for example, the second layer).
The blend and the UV absorption agent that comprise fluoropolymer, urethane polymer, acrylic ester polymer, PC, PMMA, CoPMMA or PMMA and PVDF for the preparation of the exemplary materials of the optical layers (for example, the 3rd optical layers) that absorbs UV light.
Multi-layer optical film described herein can use general treatment technology to make, and for example US Patent No 6,783, described in 349 people such as () Neavin those, the disclosure of this patent is incorporated herein by reference.
Be used for providing the desirable technique of the multi-layer optical film with controlled spectrum to comprise the layer thickness value of using the axostylus axostyle well heater to control the coextrusion polymer layer, for example as U.S. Patent number 6,783, described in No. 349 people such as () Neavin; By using the layer thickness survey instrument, for example atomic force microscope (AFM), transmission electron microscope or scanning electronic microscope, during preparation feedback layer thickness distribution in time; Optical modeling for generation of required layer thickness profile; And repeat axostylus axostyle based on the difference between the distribution of survey layer and required layer distribution and regulate.
The basic skills that layer thickness profile is controlled relates to according to the difference of destination layer thickness distribution and measured layer thickness profile adjusts axostylus axostyle district's power setting.At first the increase of regulating the required axostylus axostyle power of layer thickness value in given feedback areas can calibrate with every nanometer heat input (watt) of the gained variation in thickness of the layer that generates in this heater area.For example, use 24 axostylus axostyle districts for 275 floor can realize that the precision of spectrum controls.In case through calibration, just can be in the situation that required power adjustment be calculated in given target distribution and measured distribution.Repeat this process until two distributions are reached an agreement.
The layer thickness profile (layer thickness value) of multi-layer optical film described herein that is reflected in the incident UV light of at least 50% in designated wavelength range can be adjusted to linear distribution roughly, wherein first (the thinnest) optical layers is adjusted to 300nm light is had approximately 1/4 wavelength optical thickness (specific refractory power multiply by physical thickness) and advances to thickest layer, and described thickest layer can be adjusted to has the approximately thick optical thickness of 1/4 wavelength to 400nm light.
Some embodiment of multi-layer optical film described herein have the UV transmission belt edge in 10% to 90% transmission range, cross over less than 20 nanometers (in certain embodiments less than 10 nanometers).
The thickness of the exemplary thickness of multi-layer optical film described herein is in the scope of 25 microns to 250 microns.The exemplary thickness of the optical layers (for example, the 3rd optical layers) that absorbs has 10 microns collective's thickness in 200 micrometer ranges.
Other available aggretion type base materials comprise the base material that UV is stable, for example from making by adding UV absorption agent, antioxidant and hindered amine as light stabilizer and/or passing through the intrinsic weathering resistance (for example, fluoropolymer) of polymkeric substance film or the parts that keep generally the polymer of its optics and mechanical property in its process that is exposed to out of doors daylight and key element at least within the time period of 10 years.
Sunlight (the especially ultraviolet radiation of 280nm to 400nm) can cause the deteriorated of plastics, this so that cause colour-change and optics and degraded in mechanical properties.Suppressing photo-oxidation deteriorated is important for the open air application of mandatory requirement long durability wherein.(for example) polyethylene terephthalate, significantly increases lower than 320nm the time from about 360nm the UV Optical Absorption, and very outstanding lower than 300nm the time.The UV light of PEN strong absorption 310-370nm scope absorbs afterbody and extends to approximately 410nm, and absorbs maximum value and appear at 352nm and 337nm place.Splitting of chain betides in the situation that has oxygen, and main photo-oxidation product is carbon monoxide, carbonic acid gas and carboxylic acid.Except the direct photodissociation of ester group, also must consider oxidizing reaction, it forms carbonic acid gas equally via peroxide radical.
Therefore, may need in certain embodiments to comprise that the UV absorption layer is to protect base material (for example, multi-layer optical film) by reflection UV light, absorption UV light, scattering UV light or their combination.Usually, the UV protective layer can comprise any can be in reflection, scattering or stand for a long time the polymer composition of UV radiation when absorbing the UV radiation.The example of this base polymer comprises PMMA, organosilicon thermoplastics, fluoropolymer and their multipolymer and blend thereof.Exemplary UV absorption layer comprises the PMMA/PVDF/UVA blend.
Can mix multiple optional additive so that it absorbs UV in optical layers.The example of this additive comprises at least a in UV absorption agent, hindered amine as light stabilizer or their antioxidant.
In certain embodiments, the UV absorption agent of special expectation is red shift UV absorption agent (RUVA), and it is absorbed in 180nm UV light of (in certain embodiments, at least 80%, particularly preferably higher than 90%) in the wavelength region may of 400nm at least 70%.Usually, expectation RUVA highly dissolve in polymkeric substance, have high absorption, light lasting and within being used for the temperature range of 200 ℃ to 300 ℃ of extrusion for heat-staple, to form protective layer.If RUVA can solidify by UV, gamma ray curing, electrocuring or curing process and monomer copolymerization form supercoat, they are also very suitable.
RUVA has the spectrum fraction of coverage of increase usually in long wave UV zone, can stop the long wavelength UV light that can cause the polyester yellowing.The thickness of typical UV protective layer is in 13 microns to 380 microns (0.5 mil is to 15 mils) scopes, and the RUVA loadings is 2-10%.Other preferred benzotriazoles comprise 2-(2-hydroxyl-3,5-two-α-cumyl phenyl)-2H-benzotriazole, 5-chloro-2-(the 2-hydroxyl-3-tertiary butyl-5-aminomethyl phenyl)-2H-benzotriazole, 5-chloro-2-(2-hydroxyl-3,5-two-tert-butyl-phenyl)-2H-benzotriazole, 2-(2-hydroxyl-3,5-two-tert-pentyl phenyl)-2H-benzotriazole, 2-(2-hydroxy-3-alpha-cumyl--uncle's 5-octyl phenyl)-2H-benzotriazole, 2-(the 3-tertiary butyl-2-hydroxy-5-methyl base phenyl)-5-chloro-2H-benzotriazole.Preferred RUVA in addition comprises 2 (4,6-phenylbenzene-1-3,5-triazine-2-yl)-5-hexyloxy-phenol.Other exemplary UV absorption agents comprise can trade(brand)name " TINUVIN 1577 ", " TINUVIN 900 " and " TINUVIN 777 " derive from (the Ciba Specialty Chemicals Corporation of Ciba company of New York Ta Lidun, Tarrytown, NY) those.Preferred UV absorption agent comprises can trade(brand)name " PMMA (TA11-10 MB01) ", " PC (TA28-09 MB02) " and " PET (TA07-07MB01) " derives from the biphenyl triazine of Sukarno company (Sukano) as the masterbatch enriched material.In addition, the UV absorption agent can use with hindered amine as light stabilizer (HALS) and antioxidant combination.Exemplary HALS comprise can trade(brand)name " CHIMASSORB 944 " and " TINUVIN 123 " derive from those of Ciba company (Ciba Specialty Chemicals Corporation).Exemplary antioxidant comprise can trade(brand)name " IRGANOX 1010 " and " ULTRANOX 626 " derive from equally those of Ciba company (Ciba Specialty Chemicals Corporation).
In certain embodiments, it is multi-layer optical film that UV filters (protection) layer, and the approximately optical wavelength of 400nm (in certain embodiments, 300nm is to 400nm) is arrived in its reflection approximately 350nm.In these embodiments, the polymkeric substance of UV absorption layer does not preferably absorb the UV light of 300nm in the 400nm scope.The example of the material that this embodiment is desirable comprises PMMA/THV, PET/SPOX, PMMA/SPOX, uses polyolefin copolymer (EVA), TPU/THV and the TPU/SPOX of THV modification.In one exemplary embodiment, to derive from the THV of Dyneon LLC (Oakdale, MN) and PMMA one with trade(brand)name " DYNEON THV 220 GRADE " and " DYNEON THV 2030 GRADE " is used from the multilayer UV speculum of reflection 300-400nm or is used from the multilayer mirror of reflection 350-400nm with PET one.
Other additives can be contained in UV absorption layer (for example, UV protective layer).Non-pigmented particulate oxide zinc and titanium oxide also can be used as stopping or the scattering additive in the UV absorption layer.For example, nanometer particle can be scattered in polymkeric substance or coating matrix, with the UV radiation deteriorated be down to minimum.Nanometer particle is transparent to visible light, scattering simultaneously or the harmful UV radiation of absorption, thus minimizing is to the infringement of thermoplastics.U.S. Patent No. 5,504,134 people such as () Palmer described by use diameter approximately 0.001 micron to about 0.2 micrometer range the metal oxide particle of (more preferably approximately 0.01 micron to about 0.15 micrometer range) weaken because of the radiation-induced polymeric substrate of UV deteriorated.U.S. Patent No. 5,876,688 (Laundon) have described the method for preparing micronized zinc oxide, thereby described micronized zinc oxide is enough little is transparent in mixing oil-feed paint, coating, finish paint, plastics, makeup etc. as UV blocking agent and/or scattering diluent the time, and micronized zinc oxide is highly suitable in the present invention and uses.These fine particle of granularity in the 10-100nm scope that can weaken the UV radiation (for example, zinc oxide and titanium oxide) can derive from for example (the Kobo Products of Ke Bo Products Co., Ltd of New Jersey Nan Pulun Field, Inc., South Plainfield, NJ).Fire retardant also can be used as additive and adds in the UV protective layer.
Except UV absorption agent, HALS, nanometer particle, fire retardant and antioxidant are added to the UV absorption layer, UV absorption agent, HALS, nanometer particle, fire retardant and antioxidant can also be added to multilayer optical layer and any optional durable top coat.Also fluoresce molecule and white dyes can be added to UV absorption layer, multilayer optical layer, optional hard coat film layer or their combination.
Required UV protective layer thickness depends on the optical density(OD) target under the specific wavelength that is calculated by the Beers law usually.In certain embodiments, the optical density(OD) of UV protective layer at the 380nm place greater than 3.5,3.8 or 4; At the 390nm place greater than 1.7; At the 400nm place greater than 0.5.Persons of ordinary skill in the art will recognize that optical density(OD) should keep appropriateness constant in long goods length of life usually, in order to the defencive function of expection is provided.
Can select UV protective layer and any optional additive to realize required defencive function in the Salar light-gathering speculum, for example UV protection, property easy to clean and weather resistance.Persons of ordinary skill in the art will recognize that the above-mentioned purpose that exists multiple means to realize the UV protective layer.For example, can add the additive that is soluble in very much in some polymkeric substance to composition.The persistence of additive in polymkeric substance particularly importantly.Additive should not make polymer deterioratoin or move out of polymkeric substance.In addition, layer thickness can change to realize required protection effect.For example, thicker UV protective layer can be realized identical UV absorption level with lower UV concentration of absorbing, and provide higher UV absorbent properties because less UV absorption agent moves motivating force.A kind of mechanism that detects the change of physical property is to use the aging circulation (its disclosure is incorporated herein by reference) of describing in ASTM G155-05a (in October, 2005) and the D65 light source of working under reflective-mode.Under described test, and when the UV protective layer is applied to goods, obviously ftracture in beginning, peel off, before layering or muddiness, using CIE L *a *b *The b that the space obtains *Value increases and to be no more than 5, to be no more than 4, to be no more than 3 or be no more than before 2, and goods should stand under 340nm at least 18,700kJ/m 2Exposure.In a kind of exemplary pattern of this test, according to ASTM G155-05a (in October, 2005), goods are exposed to the xenon arc lamp weatherometer and reach 3000 hours, when with the spectrophotometer ((Perkin-Elmer of Perkinelmer Inc. that can trade(brand)name " LAMBDA 950 " derives from the Waltham, Massachusetts, Inc., Waltham, when MA)) measuring, b *Change less than 5 units.
On it, substrate surface of coating composition composition can have textured surface, and described textured surface can provide or can be added to the surface of base material when making base material.In certain embodiments, antireflecting textured surface is microstructured surface.Textured surface can provide by technology known in the art, comprises extruding copying, impressing and cast, and is then that (if necessary) solidifies.
In general, extrude reproducer and adopt the mould that to give negative structure in polymer surfaces.Described mould can be various ways and material.Usually, the form of described mould is the volume of thin plate, roller, band or surface structuration film.Mould consists of by belonging to other material of metal or polymer class usually, but can comprise potentially pottery or other suitable materials.For metal die, that described metal is generally is diamond cutting, embossing, annular knurl, through sandblasting etc., to form described surface tissue.Structurized polymer surfaces copies formation by extruding usually, and therein, thermoplastic resin such as PMMA extrude with the extrusion equipment of standard and be fed in roll gap between machining metal die roller and rubber rollers by die head.When contacting with die surface, the polymkeric substance of melting is with quenching, and then it discharge and be wound up on a roller from the mould roller.
Another program of preparation textured surface is the acrylate functional resin of die coating UV-curable of reclining, and then removes crosslinked structured film from mould.
Another program of preparation textured surface is the heat-setting carbamate functional resin of die coating that reclines, and then removes crosslinked structured film from mould.This layer of polyurethane can self-contained polyvalent alcohol, the polycondensation preparation of the reaction mixture of polymeric polyisocyanate and catalyzer.This reaction mixture also can comprise can not polycondensation annexing ingredient, and generally comprise at least a UV stablizer.As following description, this polycondensation, or solidify, thereby generally carry out producing structurized surface in the surface of solidifying in model or mould.
Because being the condensation reaction by polyvalent alcohol and polymeric polyisocyanate, the described polyether polyols with reduced unsaturation of the disclosure forms, so they comprise urethane connection key at least.The polyether polyols with reduced unsaturation that forms in the disclosure can only comprise urethane connection key, and perhaps they can comprise other optional connection keys such as polyureas joins key, polyester connection key, polymeric amide connection key, organosilicon connection key, acrylic acid or the like connection key etc.Describe as following, these other optional connection key can appear in polyether polyols with reduced unsaturation, because they are present in the polyvalent alcohol or polyisocyanate ester material that is used to form polyether polyols with reduced unsaturation.Usually, this structurizing layer of polyurethane has the size that is enough to produce required optical effect.The thickness of this layer of polyurethane generally is no more than 10 millimeters, and is usually much thin than this.Due to economic cause, thin as far as possible structurizing layer of polyurethane is used in general expectation.Perhaps expectation will be included in the amount maximization of the polyurethane material in this structure, and expectation will consist of the substrate of structurizing layer of polyurethane but do not minimized by structurized polyurethane material amount.In some cases, this base part is sometimes referred to as " base ", because the base that its similar Yushan Hill emerges from it.
Can use diversified polyvalent alcohol.The term polyvalent alcohol comprises the hydroxyl-functional formed material, it generally comprises at least 2 terminal hydroxy group, and generally can represent with structure HO-B-OH, wherein this B group can be aliphatic group, aromatic group or comprise aliphatic group and the group of the combination of aromatic group, and can comprise multiple key or functional group, comprise extra terminal hydroxy group.Usually, HO-B-OH is dibasic alcohol or hydroxy-end capped prepolymer such as urethane, polyester, polymeric amide, organosilicon, acrylic acid or the like, or the polyureas prepolymer.
The example of available polyvalent alcohol comprises polyester polyol (for example, interior ester polyol), polyether glycol (for example, polyoxy sub alkyl polylol), polyalkylene polyvalent alcohol, their mixture and the multipolymer that is obtained by them.Polyester polyol is particularly useful.Wherein, available polyester polyol is linear and nonlinear polyester polyvalent alcohol, comprise, for example by polyethylene glycol adipate, poly butylene succinate, poly-sebacic acid hexylene glycol ester, poly-dodecanedicarboxylic acid hexylene glycol ester, polyneopentyl glycol adipate, polypropylene adipate (PPA), poly-hexanodioic acid hexanaphthene dimethyl ester, and poly-e-caprolactone make those.Aliphatic polyester polyols can for example derive from the King Industries company (King Industries, Norwalk, CT) of Connecticut State Norwalk with trade(brand)name " K-FLEX " (for example " K-FLEX 188 " and " K-FLEX A308 ").
When HO-B-OH is hydroxy-end capped prepolymer, can produce required HO-B-OH prepolymer with multiple precursor molecule.For example, polyvalent alcohol can produce hydroxy-end capped polyurethane prepolymer with reaction lower than the vulcabond of stoichiometry.the example of suitable vulcabond comprises: aromatic diisocyanate (for example, 2, the 6-tolylene diisocyanate, 2, the 5-tolylene diisocyanate, 2, the 4-tolylene diisocyanate, meta-phenylene vulcabond, p-phenylene vulcabond, methylene-bis (ortho-, meta-or p-chloro-phenyl-vulcabond), methylene radical diphenylene-4, 4 '-vulcabond, the methylene radical diphenylene vulcabond of polycarbodiimide modification, (4, 4 '-two isocyanato--3, 3 ', 5, 5 '-tetraethyl-)-biphenyl methane, 4, 4 '-two isocyanato--3, 3 '-dimethoxy-biphenyl, 5-chloro-2, the 4-tolylene diisocyanate, 1-chloromethyl-2, 4-two isocyanato-benzene, the aromatic-aliphatic vulcabond is as meta-xylylene vulcabond and tetramethyl--meta-xylylene vulcabond), aliphatic diisocyanate, as Isosorbide-5-Nitrae-two isocyanato-butane, 1,6-two isocyanato-hexanes, 1,12-two isocyanato-dodecanes, 2-methyl isophthalic acid, 5-two isocyanato-pentanes, and alicyclic diisocyanate (for example, methylene radical-two cyclohexylidene-4,4 '-vulcabond and 3-isocyanato-methyl-3,5,5-3-methyl cyclohexanol based isocyanate (isoflurane chalcone diisocyanate)).Due to the requirement to weather resisteant, generally use aliphatics and alicyclic diisocyanate.
A synthetic example of HO-B-OH prepolymer is shown in following reaction scheme 1 (wherein (CO) expression carbonyl C=O):
2HO-R 1-OH+OCN-R 2-NCO→HO-R 1-O-[(CO)N-R 2-N(CO)O-R 1-O-] nH
Reaction scheme 1
Wherein n is 1 or larger, and according to the ratio of polyvalent alcohol with vulcabond, for example, when being 2: 1, n is 1 when this.Similar reaction between polyvalent alcohol and dicarboxylic acid or dianhydride can produce the HO-B-OH prepolymer with ester linking group.
The polyvalent alcohol that each molecule has more than 2 hydroxyls can will form cross-linked resin after isocyanate reaction with difunctionality or higher official.The crosslinked polymkeric substance creep that stops formation, and help to keep desired structure.Usually, this polyvalent alcohol is that aliphatic polyester polyols (can be for example with trade(brand)name " K-FLEX " (for example, " K-FLEX 188 " and " K-FLEX A308 ") derive from King Industries (the King Industries of company of Connecticut State Norwalk, Norwalk, CT)).
Can use diversified polymeric polyisocyanate.The term polymeric polyisocyanate comprises the isocyanate-functional material, it generally comprises at least 2 terminal isocyanate groups, as the vulcabond that can represent with structure OCN-Z-NCO, wherein the Z group can be aliphatics, aromatic series, perhaps comprises the group of the combination of aliphatic group and aromatic group.the example of suitable vulcabond comprises aromatic diisocyanate (for example, 2,6-tolylene diisocyanate, 2,5-tolylene diisocyanate, 2,4 toluene diisocyanate, meta-phenylene vulcabond, p-phenylene vulcabond, methylene-bis (ortho-, meta-or p-chloro-phenyl-vulcabond), methylene radical diphenylene-4,4 '-vulcabond, the methylene radical diphenylene vulcabond of polycarbodiimide modification, (4,4 '-two isocyanato--3,3 ', 5,5 '-tetraethyl-) biphenyl methane, 4,4 '-two isocyanato--3,3 '-dimethoxy-biphenyl, 5-chloro-2,4 toluene diisocyanate and 1-chloromethyl-2,4-two isocyanato-benzene), aromatic-aliphatic vulcabond (for example, meta-xylylene vulcabond and tetramethyl--meta-xylylene vulcabond), aliphatic vulcabond (for example, Isosorbide-5-Nitrae-two isocyanato-butane, 1,6-, two isocyanato-hexanes, 1,12-, two isocyanato-dodecanes and 2-methyl isophthalic acid, 5-two isocyanato-pentanes), and alicyclic diisocyanate (for example, methylene radical-two cyclohexylidene-4,4 '-vulcabond and 3-isocyanato-methyl-3,5,5-trimethylammonium-cyclohexyl isocyanate (isoflurane chalcone diisocyanate)).Due to the requirement to weather resisteant, generally use aliphatics and alicyclic diisocyanate.To a certain degree crosslinked useful to keeping the desired structure surface.A kind of approach is to use functionality greater than 2.0 polymeric polyisocyanate.A kind of exemplary aliphatic polymeric isocyanate can trade(brand)name " DESMODUR N3300A " derives from the Beyer Co., Ltd (Bayer, Pittsburgh, PA) of Pennsylvania Pittsburgh.
Another program of preparation textured surface is heated polymerizable thing film and then makes it to contact grain roller or the embossing belt with desired structure surface, thereby give the negative pattern of described picture on surface in polymeric film.
The use of anti-reflection structure film has presented and has been reflected and does not for example arrive the minimizing of amount of light of the light absorbing elements of luminous energy absorption unit as disclosed herein.For example, such anti-reflection structure film has made conventional photovoltaic solar module be achieved approximately 3% average output power to about 7% scope increases.The anti-soil thing of the exposed surface by improving the anti-reflection structure film and anti-ly be stained with grit (being pollution resistance) and/or wear resistance, these anti-reflection structure films can help to keep this type of anti-reflection structure film to the transparency of light in the length of life of luminous energy absorption unit.Like this, described film can help to increase optical transmission to the luminous energy absorption unit.Specifically, the polymer materials at the textured surface place by crosslinking structure face more to heavens, with without more the height crosslinked same polymer material compare and with other polymer materialss (for example, urethane) the same structure face that makes is compared, described structured surface can present improved mechanical endurance (for example, anti-knock-out capability).
The structured surface of luminous energy absorption unit and especially anti-reflection structure film can be exposed to the multiple unfavourable condition from outside atmosphere.For example, the described structured surface environmental element that can be exposed to the textured surface that may damage structured surface is like rain, wind, hail, snow, ice, sand etc.In addition, long-term exposure also may cause the deteriorated of structured surface in other envrionment conditionss as heat and the UV radiation that is exposed to from the sun.For example, many aggretion type organic materialss are easy to decompose because repeatedly being exposed to the UV radiation.The luminous energy absorption unit is weighed with year as the weathering resistance of device for converting solar energy, performance degradation or performance loss occur for many years and not because the expectation material can operate.The remarkable loss of expecting this material can stand to reach the outdoor exposure of 20 years and light transmission or mechanical integrity not occurring.Typical polymer organic material can't afford to stand the loss that exposes for a long time as do not occur in 20 years out of doors light transmission or mechanical integrity.In at least some embodiment, structured surface expection have pollution resistance and/or at least about 5 years at least about in 20 years scopes and mechanical endurance that may longer (for example, at least about 25 years).In addition, because it is made by the stable polymer materials of UV, therefore described structured surface can present at least about 15 years, the about long-term UV stability of 20 years or even approximately 25 years.
In certain embodiments, textured surface is made of polymer materials (comprising crosslinked polymer materials).For transparent film, for example, in certain embodiments, the cross-linked polymer density of textured surface is higher than the rest part of film.For transparent film, for example, in certain embodiments, the crosslinked polymer density of textured surface is higher than the rest part of anti-reflection structure film.For transparent film, for example, in certain embodiments, the crosslinked polymer density of the core segment of each structure is lower than the crosslinked polymer density of textured surface.For transparent film, for example, in certain embodiments, film comprises that also structure is from the basic component of its extension, all polymer elastomer materials of each structure all have the crosslinked polymer density approximately same high with textured surface, and the crosslinked polymer density of basic component is lower than each structural polymer cross-linking density.
Transparent anti-reflection structure film can be for example makes textured surface have higher crosslinked polymer density than the rest part of structured film base material to prepare by transparent structured film base material being provided as mentioned above and then processing textured surface.The textured surface of structured film base material can for example be processed by being exposed to the further crosslinked processing (for example, electron beam irradiation is processed) that will cause crosslinked polymer materials.(for example depend on the processing used of further crosslinked crosslinked polymer materials, conventional electron beam irradiation technology) setting (for example, intensity, voltage and/or time length), can there be remaining a part of structured film base material not have described higher crosslinked polymer density.Low voltage (lower than 150kV) electron beam irradiation will produce higher cross-linking density in the surface near crosslinked polymkeric substance.For example, in processing, can select also to be arranged so that anti-reflection structure has the crosslinked polymer density approximately same high with textured surface (that is, whole anti-reflection structure is all processed to have the crosslinked polymer density approximately identical with its textured surface).Perhaps, can select to process the core segment that is arranged so that each anti-reflection structure and not have the crosslinked polymer density approximately same high with textured surface.
In certain embodiments, structured film base material vicissitudinous cross-linking density of tool on the whole thickness of film base material.For example, may have the cross-linking density gradient on the thickness of structured film base material, take the cross-linking density at the textured surface place of structured film base material as the highest take minimum as it with textured surface opposing surface.Can use low voltage for example approximately 70kV increase the cross-linking density of the surface of structured film base material to the electron beam irradiation in about 150kV scope.
In certain embodiments, surface tissue comprises prism.In certain embodiments, prism respectively be included in 15 degree to the 75 degree scopes the prism tip angle and at 10 microns the pitch to 250 micrometer ranges.In certain embodiments, prism respectively be included in 15 degree to the 75 degree scopes mean obliquity and at 10 microns the pitch to 250 micrometer ranges.In certain embodiments, the paddy-peak heights of prism at 10 microns to 250 micrometer ranges.Prism can provide by technology known in the art, comprises those described in little replica technique discussed above.
In certain embodiments, transparent film has vertically and surface tissue comprises the prism with the linear grooves longitudinally that is parallel to film.Such film can be by technology preparation known in the art (for example, by utilizing the mould of the parallel linear grooves of circumferentially providing of winding mold tool).
In addition, anti-reflection structure can comprise at least one or the combination in prismatic, pyramid, taper shape, semisphere, parabola shaped, cylindrical and tubular construction.The anti-reflection structure that comprises prism can have less than 90 degree, be less than or equal to about 60 degree, be less than or equal to about 30 degree or at about 10 degree until the about prism tip angle in 90 degree scopes.Such antireflection prism structure also can have in about 2 microns paddy-paddy or peak-peak pitches to the about 2cm scope.The anti-reflection structure that comprises prism also can have the prism tip angle to the about 75 degree scopes at about 15 degree.The anti-reflection structure that comprises prism also can have in about 10 microns pitches to about 250 micrometer ranges.
In certain embodiments, surface tissue has peak and paddy and average peak-to-valley height, wherein said sinter fuse coating has mean thickness, and the mean thickness of wherein said sinter fuse coating is at most described average peak-to-valley height half (in certain embodiments, less than described average peak-to-valley height 25%).
In certain embodiments, thus the sinter fuse coating that comprises the porous network of Nano particles of silicon dioxide can be by applying the coating composition that comprises Nano particles of silicon dioxide coating to be provided, and then to heat described coating to provide goods to provide on the anti-reflection structure surface of transparent substrate.
In certain embodiments, thus comprise Nano particles of silicon dioxide porous network sinter fuse coating can by apply on the anti-reflection structure surface of transparent substrate the coating composition that comprises Nano particles of silicon dioxide with pH that coating, wherein said coating composition are provided less than 3, and then allow Nano particles of silicon dioxide acid sintering provide goods to provide.
in certain embodiments, the sinter fuse coating that comprises the porous network of Nano particles of silicon dioxide can provide in the following manner: apply on the anti-reflection structure surface of transparent substrate comprise the core-shell silica nanoparticle coating composition so that coating to be provided, wherein each core-shell particles comprises polymer core, the shell that described polymer core is disposed in the atresia preparing spherical SiO 2 particles on polymer core holds, and the volume average particle size of wherein said atresia preparing spherical SiO 2 particles is not more than 60 nanometers (in certain embodiments, be not more than 50 nanometers, 40 nanometers, 30 nanometers, 20 nanometers, or not even greater than 10 nanometers), and then heat described coating goods are provided.
Exemplary coating composition comprises aqueous dispersion and the organic solvent dispersion of Nano particles of silicon dioxide.In certain embodiments, the coating composition that contains nanoparticle comprises: pH is less than 5 aqueous dispersion, and described aqueous dispersion comprises median size and is the Nano particles of silicon dioxide of 40 nanometers (preferably less than 20 nanometers) at the most; And pK aAcid for≤3.5 (preferred＜2.5 are most preferably less than 1).The coating that preferably contains nanoparticle comprises median size and is the aggregate of the Nano particles of silicon dioxide of 40 nanometers at the most, described aggregate comprises the porous network (being generally three-dimensional network) of Nano particles of silicon dioxide, and described Nano particles of silicon dioxide and adjacent Nano particles of silicon dioxide bonding.
The Nano particles of silicon dioxide water-based paint compositions of these acidifyings can be coated directly onto under the condition that there is no machine solvent or tensio-active agent on hydrophobic organic and inorganic substrate.The wettability of these inorganic nano-particle aqueous dispersion on hydrophobic surface (for example polyethylene terephthalate (PET) or polycarbonate (PC)) is with the pH of dispersion and the pK of acid aAnd it is different.When with HCl with described coating composition be acidified to pH=2 to 3, when even being acidified to 4 or 5 in certain embodiments, they can be coated with on hydrophobic organic substrate.By contrast, coating composition is in forming globule at the bottom of organic radical under neutrality or alkaline pH.
The Nano particles of silicon dioxide that uses in these coating compositions is generally the dispersion of Nano particles of silicon dioxide in water-based, organic solvent or in water/ORGANIC SOLVENT MIXTURES of submicron-scale.In general, the average primary particle diameter of Nano particles of silicon dioxide is 40 nanometers at the most, preferably less than 20 nanometers, more preferably less than 10 nanometers.Can use transmission electron microscope to determine mean particle size.Nano silicon described in the present invention can be spherical or aspheric.Nano particles of silicon dioxide does not preferably carry out surface modification.
Inorganic silicon dioxide colloidal sol in water medium is well-known in the art, and is commercial available.Silicon dioxide gel in water or water-alcohol solution can for example derive from the E.I.Du Pont Company (E.I.duPont de Nemours and Co., Inc., Wilmington, DE) of Wilmington, the Delaware State with trade(brand)name " LUDOX "; Derive from the Nyacol company (Nyacol Co., Ashland, MA) of Massachusetts Ya Shilan with trade(brand)name " NYACOL "; And the high ground Nalco Chemical Co (Ondea Nalco Chemical Co., Oak Brook, IL) that derives from Illinois Losec Brooker with trade(brand)name " NALCO ".A kind of available silicon dioxide gel is NALC02326, its can be used as mean particle size be 5 nanometers, pH value be 10.5 and solids content be that the silicon dioxide gel of 15 % by weight obtains.Other commercially available Nano particles of silicon dioxide comprise " NALCO 1115 " and " NALCO 1130 " that can buy from Nalco Chemical Co, can certainly be positioned at " REMASOL SP30 " and " the LUDOX SM " that can buy from E.I.Du Pont Company that the New York is buied by the Remet company of carrying card (Remet Corp.Utica, NY).
In certain embodiments, the pH of coating composition is less than 5,4.5,4,3.5,3 or even less than 3; Or in 1 to 3 scope.Such water-based paint compositions can be for example by merging dispersion acid (for example, the pK lower than described dispersion with pH that comprises Nano particles of silicon dioxide at least a＜3.5 acid) make.Exemplary acid comprises oxalic acid, citric acid, H 3PO 4, HCl, HBr, HI, HBrO 3, HNO 3, HClO 4, H 2SO 4, CH 3SO 3H, CF 3SO 3H, CF 3CO 2H or CH 3SO 2At least one in OH.
In certain embodiments, along with water evaporation and sour dense increase, the porous network of Nano particles of silicon dioxide obtains by the sour sintering of Nano particles of silicon dioxide.In certain embodiments, as an alternative or in addition, the Nano particles of silicon dioxide available heat is processed (for example, flame treating) sintering.Thermal treatment can be for example by make the structurizing base material in flame (burner) below by common approximately 1-3 second or even longer carrying out, precondition is that base material is without undergoing the condition with the melting base material.Other heating techniques also can comprise for example Infrared heaters and hot-air blower.The surface opposing with coating surface can for example lead to overcooled metallic roll or apply cooling to allow the residence time longer under flame by liquid.
In certain embodiments, the invention provides a kind of composition, described composition comprises: the water-based Continuous Liquid Phase; With the core-shell particles that is scattered in described water-based Continuous Liquid Phase, wherein each core-shell particles comprises polymer core, the shell that described polymer core is disposed in the atresia preparing spherical SiO 2 particles on polymer core holds, and wherein said atresia preparing spherical SiO 2 particles has 60 nanometers (in certain embodiments, less than 50 nanometers, 40 nanometers, 30 nanometers, 20 nanometers or even less than 10 nanometers; In certain embodiments, in the scope of 5 nanometer to 60 nanometers) volume average particle size.In certain embodiments, in composition in the relative composition of the total amount of atresia preparing spherical SiO 2 particles the weight ratio of the total amount of polymkeric substance in the scope of 85: 15 to 95: 5.In certain embodiments, composition also comprises surfactant.In certain embodiments, polymer core comprises the film forming thermoplastic polymer, and this film forming thermoplastic polymer can comprise the urethane segment.
In order to realize that hull shape becomes, the atresia preparing spherical SiO 2 particles usually should be less than polymer core, but this is not a prerequisite.For example, the volume average particle size (D50) of the comparable preparing spherical SiO 2 particles of the volume average particle size of polymer particle (D50) is larger about at least 3 times.More generally, the volume average particle size of polymer particle usually should be than the volume average particle size of preparing spherical SiO 2 particles larger about at least 5 times, at least 10 times or even at least 50 times.For typical polymer particle size, the weight ratio of relatively described one or more polymer particles of atresia preparing spherical SiO 2 particles 30: 70 to 97: 3, preferred 80: 20 to 95: 5, more preferably in the scope of 85: 15 to 95: 5.
In certain embodiments, coating composition has the pH value less than 5.In certain embodiments, coating composition does not contain acicular silica particles.
In certain embodiments, coating composition also comprises organic silane adhesive (for example, tetraalkoxysilane), tensio-active agent and/or wetting agent.
Exemplary tensio-active agent comprises anion surfactant.Available anion surfactant comprises those with following molecular structure, and described molecular structure comprises (1) at least one hydrophobic part, for example C 6-C 20Alkyl, alkylaryl and/or alkenyl group, (2) at least one anionic group, such as sulfate radical, sulfonate radical, phosphate radical, polyoxyethylene sulfate radical, polyoxyethylene sulfonate radical, polyoxyethylene phosphate radical etc., and/or the salt of (3) this anionoid group, wherein said salt comprises an alkali metal salt, ammonium salt, tertiary ammonium salt etc.The representative commercial examples of available anion surfactant comprises: sodium lauryl sulphate (can for example derive from Henkel Corp. (Henkel Inc., Wilmington, DE) of Wilmington, the Delaware State with trade(brand)name " TEXAPON L-100 "; With the Si Taipan chemical company (Stepan Chemical Co, Northfield, IL) that derives from Illinois promise Mansfield moral with " POLYSTEP B-3 "; Sodium lauryl tri(oxyethyl) sulfate (can for example derive from the Si Taipan chemical company (Stepan Chemical Co., Northfield, IL) of Illinois promise Mansfield moral with trade(brand)name " POLYSTEP B-12 "; Ammonium lauryl sulfate (can for example derive from Henkel Corp. (Henkel Inc., Wilmington, DE) of Wilmington, the Delaware State with trade(brand)name " STANDAPOL A "; And Sodium dodecylbenzene sulfonate (can be for example derives from Luo Na-Rhone-Poulenc (Rhone-Poulenc, Inc., Cranberry, NJ) in the Crane uncle of New Jersey with trade(brand)name " SIPONATE DS-10 ".For the typical concentration of Nano particles of silicon dioxide (for example, be 0.2 % by weight to 15 % by weight for total coating composition), the occupancy volume of most of tensio-active agents is less than 0.1 % by weight of coating composition, preferred approximately 0.003 % by weight to 0.05 % by weight.
Exemplary wetting agent comprises: the polyethoxylated alkyl alcohol is (can be for example with trade(brand)name " BRIJ 30 " with " BRIJ 35 derives from ICI Americas Inc (ICI Americas, Inc.); With with " TERGITOL TMN-6 " SPECIALTY SURFACTANT " derive from associating carbide and Plastics Company (Union Carbide Chemical and Plastics Co.)); The polyethoxylated alkylphenol (can for example derive from associating carbide and Plastics Company (Union Carbide Chemical and Plastics Co.) with trade(brand)name " TRITON X-100 "; Derive from not Lip river Farnham Parker's BASF AG (BASF Corp., Florham Park, NJ) of New Jersey with " ICONOL NP-70 "); And polyethylene/polypropylene glycol segmented copolymer (can for example derive from BASF AG (BASF Corp.) with trade(brand)name " TETRONIC 1502 BLOCK COPOLYMER SURFACTANT ", " TETRONIC 908 BLOCK COPOLYMER SURFACTANT " and " PLURONIC F38 BLOCK COPOLYMER SURFACTANT ").In general, according to the amount of Nano particles of silicon dioxide, the consumption of wetting agent lower than 0.1 % by weight of coating composition, be preferably 0.003 % by weight to 0.05 % by weight of coating composition.Clean in water or flood and to be conducive to remove excessive tensio-active agent or wetting agent through coated article.
In certain embodiments, the median size that is used for the nanoparticle of goods and coating composition is 500 nanometers at the most, 400 nanometers, 300 nanometers, 200 nanometers, 150 nanometers, 100 nanometers, 75 nanometers, 50 nanometers, 40 nanometers, 30 nanometers or 20 nanometers even at the most.
In certain embodiments, the nanoparticle for goods and coating composition has bimodal distribution.In certain embodiments, first of the bimodal distribution of nanoparticle be distributed in 2 nanometer to 15 nanometer range, second be distributed in 20 nanometer to 500 nanometer range; First be distributed in 2 nanometer to 20 nanometer range, second be distributed in 30 nanometer to 500 nanometer range, perhaps even first be distributed in 5 nanometer to 15 nanometer range, second be distributed in 20 nanometer to 100 nanometer range.On the other hand, in certain embodiments, the weight ratio of the first relative the second distribution nanoparticle of distribution nanoparticle is in the scope of 1: 99 to 99: 1,10: 90 to 90: 10,20: 80 to 80: 20 or even 30: 70 to 70: 30.
Comprise for the technology that applies coating composition and use roller coat, spraying, curtain coating, dip-coating and air knife.
In certain embodiments, thus maybe advantageously use technology corona known in the art or flame treating base material can strengthen the wettability of the surface with coating composition to be coated to improve the surface.
In certain embodiments, the coating of sintering is conformal coating with respect to the anti-reflection structureization surface of transparent substrate.Corona or the flame treating on the surface with coating composition to be coated can help to obtain conformal coating.
In certain embodiments, the coating specific surface structure of sintering is from have higher optical transmittance on wider incident angle of light scope.Although do not want to be bound by theory, it is believed that porous nano silica provides extra anti-reflective because of graded index (porosity of surface is higher).In addition, it is believed that the incident angle of light outside the critical angle of prism slope will reduce the optical transmittance with raising because of the reflection that graded index porous nano silica coating provides.
Not accumulating in the lip-deep dirt of anti-reflection structureization described herein and the grit that comprise Nano particles of silicon dioxide will be more easy to clean.
Referring to Fig. 4, exemplary transparent configuration surface film 40 comprises structured film base material 43, and structured film base material 43 has main structure face 42, and main structure face 42 has the textured surface of the form that is prism rib 41.Each textured surface 41 has the tip angle α less than 90 degree.Film 40 also has textured surface 41 from the basic component 45 of its extension.Basic component 45 can be as shown in the figure forms as the part of structure 41, perhaps can form as independent layer as shown in dotted line 48.Structured surface 44 also is coated with Nano particles of silicon dioxide 46 on surface 44, Nano particles of silicon dioxide 46 can be sintered.Supporting backing 45 can be for example polymer materials, glass or other transparent ceramic materials.Exemplary polymer materials can comprise polymethylmethacrylate (PMMA) film, poly(vinylidene fluoride) (PVDF) film, PMMA/PVDF/UVA blend membrane, polyethylene terephthalate (PET) film, scribble PET film, the polycarbonate membrane of priming paint, have the three strata carbonic ether films on PMMA/PVDF/UVA blend top layer, at least one or combination in crosslinked polyurethane film, acrylate films, ethylene fluoride-propylene (FEP) film or UV mirror film.Optional binder layer 49 is opposing with textured surface face 44.
Referring to Fig. 5, exemplary transparent configuration surface film 50 has structured film base material 55, and structured film base material 55 has main structure face 52, and main structure face 52 has the textured surface of the form that is prism rib 53.Each textured surface 53 has the tip angle β less than 90 degree.Film 50 comprises that also textured surface 53 is from the basic component 54 of its extension.Basic component 55 can be as shown in the figure forms as the part of structure 53, perhaps can form as independent layer as shown in dotted line 58.Exposed structure face 53 makes core or the rest part 54 of the crosslinked polymer density ratio structured film base material 54 of each textured surface 53 want high in other crosslinking Treatment (for example, electron beam irradiation or heat energy).Exposure strength and/or the time length of depending on for example other crosslinking Treatment than the degree of depth of high crosslink density.That has observed textured surface 53 makes the anti-soil thing be stained with the grit raising with resisting than high crosslink density.Advantageously film 50 as herein described or any other structured surface film comprise the coating of porous silicon dioxide nano particle 51 on surface 53, and porous silicon dioxide nano particle 51 can be sintered.Supporting backing 55 can comprise for example polymer materials or glass or other transparent ceramic materials.Exemplary polymer materials can comprise polymethylmethacrylate (PMMA) film, poly(vinylidene fluoride) (PVDF) film, PMMA/PVDF/UVA blend membrane, polyethylene terephthalate (PET) film, scribble PET film, the polycarbonate membrane of priming paint, have the three strata carbonic ether films on PMMA/PVDF/UVA blend top layer, at least one or combination in crosslinked polyurethane film, acrylate films, ethylene fluoride-propylene (FEP) film or UV mirror film.Optional binder layer 59 is opposing with textured surface face 53.
Referring to Fig. 6, exemplary transparent configuration surface film 60 has structured film base material 63, and structured film base material 63 has main structure face 62, and main structure face 62 has the textured surface of the form that is prism rib 61.Each textured surface 61 has the tip angle θ less than 90 degree.Film 60 also has textured surface 61 from the basic component 63 of its extension.Structured surface 61 also is coated with porous silicon dioxide nano particle 64 on surface 61, porous silicon dioxide nano particle 64 can be sintered.Supporting backing 63 can comprise for example polymer materials or glass or other transparent ceramic materials.Exemplary polymer materials can comprise polymethylmethacrylate (PMMA) film, poly(vinylidene fluoride) (PVDF) film, PMMA/PVDF/UVA blend membrane, polyethylene terephthalate (PET) film, scribble PET film, the polycarbonate membrane of priming paint, have the three strata carbonic ether films on PMMA/PVDF/UVA blend top layer, at least one or combination in crosslinked polyurethane film, acrylate films, ethylene fluoride-propylene (FEP) film or UV mirror film.
Referring to Fig. 7, exemplary transparent configuration surface film 70 has structured film base material 75, and structured film base material 75 has main structure face 72, and main structure face 72 has the textured surface of the form that is prism rib 71.Each textured surface 71 has the tip angle γ less than 90 degree.Film 70 also has textured surface 71 from the basic component 75 of its extension.Basic component 75 can be as shown in the figure forms as the part of structure 71, perhaps can form as independent layer as shown in dotted line 78.Exposed structure face 71 makes core or the rest part 74 of the crosslinked polymer density ratio structured film base material 74 of each textured surface 71 want high in other crosslinking Treatment (for example, electron beam irradiation or heat energy).Have exposure strength and/or the time length of depending on other crosslinking Treatment than the depth D of high crosslink density.That has observed textured surface 71 makes the anti-soil thing be stained with grit raising and wear resistance raising with resisting than high crosslink density.Film 70 as herein described or any other structured surface film have the coating of porous silicon dioxide nano particle 79 on surface 71, porous silicon dioxide nano particle 79 can be sintered.Supporting backing 75 can comprise for example polymer materials or glass or other transparent ceramic materials.Exemplary polymer materials can comprise polymethylmethacrylate (PMMA) film, poly(vinylidene fluoride) (PVDF) film, PMMA/PVDF/UVA blend membrane, polyethylene terephthalate (PET) film, scribble PET film, the polycarbonate membrane of priming paint, have the three strata carbonic ether films on PMMA/PVDF/UVA blend top layer, at least one or combination in crosslinked polyurethane film, acrylate films, ethylene fluoride-propylene (FEP) film or UV mirror film.Optional binder layer 76 is opposing with textured surface face 71.
Fig. 8 is the camera digital picture of the cross section of the exemplary acids fused silica nanoparticle that is coated with on the anti-reflecting surface structure.Transparent configuration surface film base material 83 has textured surface prism 82, and prism 82 has the tip angle less than 90 degree
Figure BPA00001701421000301
The face of each prism is coated with the layer 81 of porous silica.Supporting backing 83 and textured surface 82 can comprise for example PMMA.
Fig. 9 has illustrated to have the anti-soil thing characteristic of concentration of raising and the exemplary circular rib prismatic surface geometrical shapes of wear resistance by sandblast.Each textured surface has the drift angle 91 less than 90 degree.Textured surface has the pitch 92 of being separated by and being no more than 1mm usually.Peak-to-valley height 93 is no more than 1mm usually.Peak and/or paddy radius 94 are generally at least 1 micron.
Because some embodiment of goods described herein are used in outdoor application, therefore weathering resistance is a desired characteristic of goods.Accelerated deterioration research is a selection estimating product properties.Accelerated deterioration research for example can be used and ASTM G-155-05a (in October, 2005), those similar technology of describing in " Standard practice for exposing non-metallic materials in accelerated test devices that use laboratory light sources (using the standard implementation rules of non-metallic material exposure in the acceleration test apparatus of laboratory light source) " are carried out on film, and the disclosure of described standard is incorporated herein by reference.
In certain embodiments, the optical transmittance of film after the following staining test of experience changes less than 8%.
Staining test
Use is from 95 square millimeters of plastic skin formula culture dish (Becton Dickinson Labware (Becton Dickinson Labware of company that can trade(brand)name " FALCON 35112 " derives from Franklin, New Jersey lachs, Franklin Lakes, NJ)) the device experiment coating stain resistance of structure, the Lower Half of skin formula culture dish drills through the hole of a 5cm.Take advantage of the coated sample of 8cm to stick to the hole that covers 5cm on the outside of skin formula culture dish a 5cm with adhesive tape, the coating surface that makes sample is towards the inside of skin formula culture dish and directly be exposed to the test dirt.(the 0-600 micron distributes with 50 gram Arizona test dust; Can derive from the powder technology company (Powder Technology Incorporated, Burnsville, MN) of Minnesota State Burns Wei Er) be placed in the Lower Half of skin formula culture dish, thus cover described coated sample.Merge securely the two halves of petri diss and jiggle with the circulation of vacillating now to the left, now to the right, making the dirt rollback that comes up on the surface of sample moving.Rock sample with hand, with lasting 60 circulations of the speed of 1 circulation of per second with vacillating now to the left, now to the right.Then take off sample and tapped adheres to get not tight dirt to remove from testing apparatus.Before and after the filth test with the transmittance of hazemeter (can trade(brand)name " HAZE GARD PLUS " derive from the Maryland State Colombian BYK-Gardner company (BYK-Gardner, Columbia, MD)) measurement coated sample.After filth test, rinse gently under water sample to remove dirt and dry, again measure transmittance measuring as cleanablity.
In certain embodiments, the optical transmittance of film after the following sand trial of experience changes less than 8%.
Sand trial
Use falling sand abrasion test machine (the big vast fort German system that can trade(brand)name " HP-1160 " derives from the Norwich, Illinois is made company (Humboldt MFG.Co., Norridge, IL)) testing coating wear resistance.Take advantage of the coated sample of 8cm to append to a 5cm with adhesive tape and be centered at the following test platform of knockout pipe outlet.Toward the 1000 gram ASTM C778 quartz sands of packing in the hopper of knockout pipe charging (can derive from the U.S. silica company (U.S.Silica Company, Ottawa, IL) in Ottawa, Illinois).Open the sluices, sand begins by the distance of knockout pipe whereabouts 100cm and strikes on the surface of coated sample.Measure the transmittance of coated sample with hazemeter (" HAZE GARD PLUS ") before and after sand trial.After sand trial, also rinse gently under water sample also dry to remove chip, and again measure transmittance.
Can be with some embodiment and the transparent supporting backing combination with interarea of goods described herein, wherein said transparent supporting backing dissipation static, and the structurizing base material comprises that also the backing face of the interarea that is bonded to the supporting backing is to form the anti-reflection structure goods that strengthen.Transparent supporting backing also can be selected to dissipate, and (for example, the supporting backing can comprise and makes can dissipate one or more polymer materialss of static of supporting backing static.for example, transparent supporting backing also can comprise inherently the electrostatically dissipative polymkeric substance such as urethane (can for example derive from (the Lubrizol Corp. of Lubrizol Corp. of Ohio Wyclif with trade(brand)name " STATRITE X5091 ", Wickliffe, OH)), polymethylmethacrylate (can for example derive from Lubrizol Corp. (Lubrizol Corp.) with trade(brand)name " STATRITE M809 ") or PMMA (can for example derive from the RTP (RTP of company of Minnesota State Wei Nuona with trade(brand)name " PERMASTAT ", Winona, MN)) and the polymkeric substance that can be blended into to prepare transparent supporting backing (for example, poly(vinylidene fluoride) (PVDF)) the electrostatically dissipative salt in (can for example derive from (the 3M Company of 3M company in Sao Paulo, the Minnesota State with trade(brand)name " FC4400 ", St.Paul, MN)).In addition or as an alternative, the structured film base material can comprise this type of electrostatically dissipative salt.
Replace the supporting backing or except the supporting backing, also maybe advantageously film as herein described or any other transparent anti-reflection structure film to be used in combination with optional moisture barrier.In such embodiments, moisture barrier can be for example by laminated, coating or the moisture-resistant blocking layer is bonded to indirectly or directly via one or more middle layers (for example, support back lining) on the main backing face of structured film base material and forms.Perhaps, moisture barrier can form to demonstrate moisture barrier character (for example, to suppress moisture absorption, infiltration etc.) by the composition of preparation film.
Moisture barrier can be for example for being disclosed in U.S. Patent No. 7,486,019 (people such as Padiyath) and No.7,215, disclosed barrier assembly, blocking layer in 473 (Fleming), U.S. Patent application No.US 2006/0062937 A1 that announces and international patent application No.PCT/US2009/062944, the disclosure of described patent is incorporated herein by reference.Moisture barrier can be available, because organosilicon has high wetting vapour transmitance, and photovoltaic cell is generally moisture-sensitive.Therefore, by carrying out backing with moisture barrier, transparent anti-reflection structure film of the present invention can be directly in the upper use of the photovoltaic cell (for example, copper/indium/gallium/selenium or CIGS photovoltaic cell) of moisture-sensitive.
Can be used for implementing barrier film of the present invention and can be selected from multiple structure.Barrier film usually is chosen as and makes them have oxygen and the water transmitance of using desired prescribed level.In certain embodiments, the water vapor transmission rate (WVTR) of barrier film (WVTR) under 38 ℃ and 100% relative humidity lower than about 0.005g/m 2/ day; In certain embodiments, under 38 ℃ and 100% relative humidity lower than about 0.0005g/m 2/ day; And in certain embodiments, under 38 ℃ and 100% relative humidity lower than about 0.00005g/m 2/ day.In certain embodiments, under 50 ℃ and 100% relative humidity, the WVTR of flexible barrier film is lower than approximately 0.05,0.005,0.0005 or 0.00005g/m 2/ day or under 85 ℃ and 100% relative humidity even lower than approximately 0.005,0.0005,0.00005g/m 2/ day.In certain embodiments, the OTR oxygen transmission rate of barrier film under 23 ℃ and 90% relative humidity lower than about 0.005g/m 2/ day; In certain embodiments, under 23 ℃ and 90% relative humidity lower than about 0.0005g/m 2/ day; And in certain embodiments, under 23 ℃ and 90% relative humidity lower than about 0.00005g/m 2/ day.
Exemplary available barrier film comprises the mineral membrane by ald, thermal evaporation, sputter and chemical Vapor deposition process preparation.Available barrier film is normally flexible and transparent.
In certain embodiments, available barrier film comprises inorganic/organic multilayer.For example, U.S. Patent number 7,018 has been described the super barrier film of the flexibility that comprises inorganic/organic multilayer in 713 (people such as Padiyath).This type of flexible super barrier film can have the first polymer layer that is arranged on the polymeric film base material, and two or more inorganic barrier layers that this polymeric film base material is separated by at least one the second polymer layer are pushed up to be coated with.In certain embodiments, barrier film comprises an inorganic barrier layer, and it is inserted between the first polymer layer and the second polymer layer that is arranged on the polymeric film base material.
The first and second polymer layers can independently form, way is: the layer and the crosslinked described layer that apply monomer or oligopolymer form polymkeric substance with original position, for example, by flash distillation and the vapour deposition of radiation-cross-linkable monomer, then for example come crosslinked with electron beam device, UV light source, electric discharge device or other suitable devices.The first polymer layer is coated to the polymeric film base material, and the second polymer layer is applied to inorganic barrier layer usually.The materials and methods that can be used for forming described the first and second polymer layers can be chosen as identical or different independently.can be used for flash distillation and vapour deposition, then in-situ cross-linked technology is found in for example U.S. Patent number 4,696,719 (Bischoff), 4,722,515 (Ham), 4,842,893 (people such as Yializis), 4,954,371 (Yializis), 5,018,048 (people such as Shaw), 5,032,461 (people such as Shaw), 5,097,800 (people such as Shaw), 5,125,138 (people such as Shaw), 5,440,446 (people such as Shaw), 5,547,908 (people such as Furuzawa), 6,045,864 (people such as Lyons), 6,231,939 (people such as Shaw) and 6,214,422 (Yializis), in disclosed PCT patent application WO No. 00/26973 (Delta V Technologies company), D.G.Shaw and M.G.Langlois, " A New Vapor Deposition Process for Coating Paper and Polymer Webs " (a kind of novel gas-phase deposition for coated paper web and polymer web) is in the 6th international vacuum coating meeting (6th International Vacuum Coating Conference) (1992), D.G.Shaw and M.G.Langlois, " a kind of novel high speed technique for the vapour deposition acylate film: upgraded edition (A New High Speed Process for Vapor Depositing Acrylate Thin Films:An Update) " is in Society of Vacuum Coaters 36th Annual Technical Conference Proceedings (the 36th technology nd Annual Meeting collection of vacuum coater association) (1993), D.G.Shaw and M.G.Langlois, " Use of Vapor Deposited Acrylate Coatings to Improve the Barrier Properties of Metallized Film " (the vapour deposition acrylate coatings is for purposes of the barrier properties of improving metalized film) is in the 37th technology nd Annual Meeting collection of vacuum coater association (Society of Vacuum Coaters 37th Annual Technical Conference Proceedings) (1994), D.G.Shaw, M.Roehrig, M.G.Langlois and C.Sheehan, " Use of Evaporated Acrylate Coatings to Smooth the Surface of Polyester and Polypropylene Film Substrates " (the evaporation acrylate coatings is used for the purposes on the surface of level and smooth polyester and polypropylene screen substrate) is in international radiation curing tissue (RadTech) (1996), J.Affinito, P.Martin, M.Gross, C.Coronado and E.Greenwell, " Vacuum deposited polymer/metal multilayer films for optical application " (the vacuum moulding machine polymer/metal multilayer film that is used for optical application), solid film (Thin Solid Films) 270 is in 43-48 (1995), and J.D.Affinito, M.E.Gross, C.A.Coronado, G.L.Graff, E.N.Greenwell and P.M.Martin, " Polymer-Oxide Transparent Barrier Layers " (polymkeric substance-oxidic transparent blocking layer) is in the 39th technology nd Annual Meeting collection of vacuum coater association (Society of Vacuum Coaters 39th Annual Technical Conference Proceedings) (1996).In certain embodiments, polymer layer and inorganic barrier layer successive sedimentation and do not interrupt coating process in one way vacuum coated operation.
The coating efficiency of the first polymer layer can improve by for example cooling polymer film base material.Also can improve with similar techniques the coating efficiency of the second polymer layer.Also can apply with conventional coating process such as roller coat (for example, intaglio plate roller coat) or spraying (for example, electrostatic spraying) and can be used for forming described first and/or monomer or the oligopolymer of the second polymer layer.Described first and/the second polymer layer also can form by being applied to the layer that contains oligopolymer or polymkeric substance in solvent and then using routine techniques (for example in heat or vacuum at least a) to remove solvent.Also can adopt plasma polymerization.
Volatilizable acrylate and methacrylate monomer can be used for forming described the first and second polymer layers.In certain embodiments, use volatilizable acrylate.The molecular weight of volatilizable acrylate and methacrylate monomer can be approximately 150 in about 600 g/mols of scopes, or in certain embodiments, approximately 200 in about 400 g/mols of scopes.In certain embodiments, in the molecular weight of volatilizable acrylate and methacrylate monomer and each molecule, the rate value of the quantity of (methyl) acrylate-functional groups is approximately 150 in about 600g/ mole/(methyl) acrylate group scope, in certain embodiments, approximately 200 in about 400g/ mole/(methyl) acrylate group scope.Can use the acrylate of fluoridizing and the methacrylic ester of high molecular scope more or ratio, for example approximately 400 to about 3000 molecular weight or approximately 400 to about 3000g/ mole/(methyl) acrylate group.exemplary available volatilizable acrylate and methacrylic ester comprise hexanediol diacrylate, the vinylformic acid ethoxy ethyl ester, the vinylformic acid phenoxy ethyl, (list) vinylformic acid cyano group ethyl ester, isobornyl acrylate, isobornyl methacrylate, the vinylformic acid stearyl, isodecyl acrylate, lauryl acrylate, propenoic acid beta-carboxyl ethyl ester, the vinylformic acid tetrahydro furfuryl ester, the dintrile acrylate, vinylformic acid pentafluorophenyl group ester, vinylformic acid nitrophenyl ester, vinylformic acid 2-phenoxy ethyl, methacrylic acid 2-phenoxy ethyl, (methyl) vinylformic acid 2,2,2-trifluoro methyl esters, diethylene glycol diacrylate, triethylene glycol diacrylate, TEGDMA, tripropylene glycol diacrylate, tetraethylene glycol diacrylate, neopentylglycol diacrylate, ethoxylated neopentylglycol diacrylate, polyethyleneglycol diacrylate, tetraethylene glycol diacrylate, the bisphenol-A epoxy diacrylate, HDDMA, Viscoat 295, ethoxylated trimethylolpropane triacrylate, the propylated Viscoat 295, three (2-hydroxyethyl) isocyanuric acid ester triacrylate, pentaerythritol triacrylate, thiophenyl ethyl propylene acid esters, naphthyloxy ethyl propylene acid esters, ring-type diacrylate (can for example derive from cyanogen secret service industry company (Cytec Industries Inc.) with trade(brand)name " EB-130 ") and tristane dimethanol diacrylate (can for example derive from (the Sartomer Co. of Sartomer company of Pennsylvania's Exton with trade(brand)name " SR833S ", Exton, PA)), epoxy acrylate (can for example derive from cyanogen secret service industry company (Cytec Industries Inc.) with trade(brand)name " RDX80095 ") and their mixture.
the monomer available that is used to form the first and second polymer layers can derive from multiple commercial source, and comprise urethane acrylate (can for example derive from Sartomer company (Sartomer Co.) with trade(brand)name " CN-968 " and " CN-983 "), isobornyl acrylate (can for example derive from Sartomer company (Sartomer Co.) with trade(brand)name " SR-506 "), Dipentaerythritol five acrylate (can for example derive from Sartomer company (Sartomer Co.) with trade(brand)name " SR-399 "), epoxy acrylate (can for example derive from Sartomer company (Sartomer Co.) with trade(brand)name " CN-120S80 ") with the vinylbenzene blend, two-trimethylolpropane tetra-acrylate (can for example derive from Sartomer company (Sartomer Co.) with trade(brand)name " SR-355 "), diethylene glycol diacrylate (can for example derive from Sartomer company (Sartomer Co.) with trade(brand)name " SR-230 "), 1,3-butylene glycol diacrylate (can for example derive from Sartomer company (Sartomer Co.) with trade(brand)name " SR-212 "), five acrylate (can for example derive from Sartomer company (Sartomer Co.) with trade(brand)name " SR-9041 "), tetramethylol methane tetraacrylate (can for example derive from Sartomer company (Sartomer Co.) with trade(brand)name " SR-295 "), pentaerythritol triacrylate (can for example derive from Sartomer company (Sartomer Co.) with trade(brand)name " SR-444 "), ethoxylation (3) Viscoat 295 (can for example derive from Sartomer company (Sartomer Co.) with trade(brand)name " SR-454 "), ethoxylation (3) Viscoat 295 (can for example derive from Sartomer company (Sartomer Co.) with trade(brand)name " SR-454HP "), alkoxylate trifunctional acrylate (can for example derive from Sartomer company (Sartomer Co.) with trade(brand)name " SR-9008 "), propylene glycol diacrylate (can for example derive from Sartomer company (Sartomer Co.) with trade(brand)name " SR-508 "), neopentylglycol diacrylate (can for example derive from Sartomer company (Sartomer Co.) with trade(brand)name " SR-247 "), ethoxylation (4) bisphenol a dimethacrylate (can for example derive from Sartomer company (Sartomer Co.) with trade(brand)name " CD-450 "), cyclohexane dimethanol diacrylate (can for example derive from Sartomer company (Sartomer Co.) with trade(brand)name " CD-406 "), isobornyl methacrylate (can for example derive from Sartomer company (Sartomer Co.) with trade(brand)name " SR-423 "), ring-type diacrylate (can for example derive from Sartomer company (Sartomer Co.) with trade(brand)name " IRR-214 ") and three (2-hydroxyethyl) isocyanuric acid ester triacrylate (can for example derive from Sartomer company (Sartomer Co.) with trade(brand)name " SR-368 "), the acrylate of aforementioned methacrylic ester and the methacrylic ester of aforementioned acrylate.
Can be used for forming described first and/or other monomers of the second polymer layer comprise vinyl ether, vinyl naphthalene, vinyl cyanide and their mixture.
The chemical constitution that the first polymer layer is required and thickness partly depend on character and the surface shape of polymeric film base material.First and/or the thickness of the second polymer layer will be enough to provide smoothly usually, defect-free surface, inorganic barrier layer can be applied to this surface subsequently.For example, the thickness of the first polymer layer can be for several nm (for example 2nm or 3nm) to approximately 5 microns or thicker.The thickness of the second polymer layer also can be in this scope, in certain embodiments, and can be thinner than the first polymer layer.
The inorganic barrier layer of visible light transmissive can be formed by multiple material.Available material comprises metal, metal oxide, metal nitride, metallic carbide, metal oxynitrides, metal oxygen boride and their combination.Exemplary metal oxide comprises: Si oxide such as silicon-dioxide, aluminum oxide such as aluminum oxide, titanium oxide such as titanium dioxide, indium oxide, tin-oxide, tin indium oxide (ITO), tantalum oxide, zirconium white, niobium oxides and their combination.Other exemplary materials comprise norbide, wolfram varbide, silicon carbide, aluminium nitride, silicon nitride, boron nitride, aluminium oxynitride, silicon oxynitride, oxynitriding boron, oxygen zirconium boride 99.5004323A8ure, oxygen titanium boride and their combination.In certain embodiments, the inorganic barrier layer of visible light transmissive comprises at least a in ITO, silicon oxide or aluminum oxide.In certain embodiments, suitably select the relative proportion of various elementary compositions, can be so that ITO conducts electricity.Can for example form inorganic barrier layer with the technology that adopts in film metallization technique, for example sputter is (for example for described technology, negative electrode or planar magnetic control sputtering, two AC planar magnetic control sputtering or the rotatable magnetron sputtering of two AC), the evaporation (for example, the energy of thermal resistance evaporation or electron beam evaporation and thermal resistance evaporation or electron beam evaporation strengthens analogue, comprises ionic fluid and plasma ion assisted deposition), chemical vapour deposition, plasma enhanced chemical vapor deposition and plating.In certain embodiments, use sputter (for example, reactive sputtering) to form inorganic barrier layer.When inorganic layer be by with the such more low-yield technology high-energy deposition technique Comparatively speaking of for example conventional gas-phase deposition for example sputter form the time, observe the barrier properties of enhancing.Be not bound by theory, the characteristic that it is believed that enhancing is that this causes because compacting causes lower hole ratio because the condensed material that arrives base material has larger kinetic energy.
The chemical constitution that each inorganic barrier layer is required and thickness partly depend on character and surface topography and the required optical property of barrier film of lower floor.Inorganic barrier layer is usually enough thick in being continuous, and enough thin to guarantee that barrier film disclosed herein and assembly have required visible transmission and flexible degree.The physical thickness of each inorganic barrier layer (with optical thickness in pairs than) can be for example approximately 3nm to about 150nm (in certain embodiments, for about 4nm to about 75nm).The term " the visible light transmissive " that this paper is used for the description inorganic barrier layer can mean to measure along normal axis, average transmittance on the visible part of spectrum is at least about 75% (in certain embodiments, at least about 80%, 85%, 90%, 92%, 95%, 97% or 98%).In certain embodiments, inorganic barrier layer is at least about 75% (in certain embodiments, at least about 80%, 85%, 90%, 92%, 95%, 97% or 98%) to 400nm to the average transmittance on the 800nm scope.The inorganic barrier layer of visible light transmissive is not hinder those layers that for example absorb visible light by photocell.
If necessary, can there be other inorganic barrier layer and polymer layer.Exist therein in the embodiment of a more than inorganic barrier layer, inorganic barrier layer needn't be identical or has identical thickness.When having a more than inorganic barrier layer, inorganic barrier layer can be called " the first inorganic barrier layer " and " the second inorganic barrier layer ".Can there be other " polymer layer " between other inorganic barrier layer.For example, barrier film can have some inorganic barrier layers that replace and polymer layer.The unit of inorganic barrier layer and polymer layer combination is called as paired layer, and barrier film can comprise any amount of paired layer.Also can comprise various types of optical layers between layer in pairs.
Can apply surface treatment or tack coat for example to improve slipperiness or adhesivity between any polymer layer or inorganic barrier layer.Available surface treatment is included in and has the discharge (as plasma body, glow discharge, corona discharge, dielectric barrier discharge or atmosphere pressure discharging) of carrying out in the situation that is fit to reactivity or non-reactive; Chemical Pretreatment; Or flame pre-treatment.Also can form independent adhesion promoting layer between the major surfaces of polymer film substrate and barrier film.For example, adhesion promoting layer can be independent polymer layer or metal-containing layer, such as metal level, metal oxide layer, metal nitride layer or metal oxynitrides layer.The thickness of adhesion promoting layer can arrive approximately 50nm or thicker for several nanometers (nm) (for example 1nm or 2nm).
In certain embodiments, available barrier film comprises plasma-deposited polymer layer (for example quasi-diamond layer), such as in U.S. Patent Application Publication 2007-0020451 (Padiyath etc.) disclosed those.For example, be coated with the first polymer layer by top on the visible light transmissive base material of flexibility, and the top is coated with plasma-deposited polymer layer on this first polymer layer, can prepare barrier film.Described the first polymer layer can be as described in the first polymer layer embodiment above any.Described plasma-deposited polymer layer can be for example quasi-diamond carbon-coating or quasi-diamond glass.Describe a layer and refer to this layer on the top of substrate or other elements with respect to the term " top is coated with " of the position of the substrate of barrier film or other elements, but not necessarily with substrate or other element adjacency.Term " quasi-diamond glass " (DLG) refers to comprise cardinal principle or the complete unbodied glass of carbon and silicon, and optionally comprises one or more additional component that are selected from hydrogen, nitrogen, oxygen, fluorine, sulphur, titanium and copper.Also can there be other element in certain embodiments.The cluster that amorphous-type diamond glassy membrane can comprise atom is to give its short range order but substantially do not cause medium and the long-range order of microcosmic or macrocrystallinity, and described microcosmic or macrocrystallinity adversely scattering wavelength are that 180nm is to the radiation of 800nm.Term " diamond-like carbon " (DLC) refers to amorphous membrance or coating, it comprises the carbon of about 50 to 90 atom % and the about hydrogen of 10 to 50 atom %, grammeatom density approximately 0.20 to every cubic centimetre of about 0.28 grammeatom, and by approximately 50% consisting of to about 90% tetrahedral bonds.
In certain embodiments, barrier film can have by the top and is coated in a plurality of layers that the DLG that replaces on flexible visible light transmissive base material or DLC layer and polymer layer (for example, the first and second polymer layers) are as mentioned above made.The unit that comprises the combination of polymer layer and DLG or DLC layer is called as paired layer, and described assembly can comprise any amount of paired layer.Also can comprise various types of optical layers between layer in pairs.Add more layer can improve it to impermeability of oxygen, moisture or other pollutents in barrier film and can also help to hide or sealer coat in defective.
In certain embodiments, on the basis without hydrogen, quasi-diamond glass comprises at least 30% carbon, a large amount of silicon (usually at least 25%) and is no more than 45% oxygen.Quite the unique combination of the oxygen of the silicon of a large amount and significant quantity and a large amount of carbon makes these film highly transparents and is flexible.The quasi-diamond glass film can have the multiple light-transmission characteristic.According to composition, film can have the light transmission features of enhancing in various frequencies.But in certain embodiments, film (when thick approximately a micron time) to about 250nm the radiation transmission at least 70% under the basic all wavelengths of about 800nm (for example 400nm to approximately 800nm).For the film of a micron thickness, in the visible wavelength region between 400nm to 800nm, 70% transmissivity is corresponding to less than 0.02 optical extinction coefficient (k).
When producing the quasi-diamond glassy membrane, can mix multiple annexing ingredient and change and strengthen the quasi-diamond glassy membrane and give the character of substrate (for example stopping and surface properties).Annexing ingredient can comprise one or more in hydrogen, nitrogen, fluorine, sulphur, titanium or copper.Other annexing ingredient also can have beneficial effect.The interpolation of hydrogen has promoted the formation of tetrahedral bonds.The interpolation of fluorine can strengthen stopping of quasi-diamond glassy membrane and surface properties, is included in the ability of disperseing in inconsistent matrix.The source of fluorine comprises for example tetrafluoro-methane (CF 4), sulfur hexafluoride (SF 6), C 2F 6, C 3F 8And C 4F 10Compound.The interpolation of nitrogen can be used to strengthen oxidation-resistance and increases specific conductivity.The source of nitrogen comprises nitrogen (N 2), ammonia (NH 3) and hydrazine (N 2H 6).The interpolation of sulphur can improve adhesivity.The interpolation of titanium tends to strengthen adhesion and diffusion and barrier properties.
Can use multiple additives in the DLC film.Except for top to quasi-diamond glass described former thereby the nitrogen or fluorine that add, can also add oxygen and silicon.Silicon and oxygen are added into optical clarity and the thermostability that the DLC coating is often improved coating.The source of oxygen comprises oxygen (O 2), water vapour, ethanol and hydrogen peroxide.The source of silicon preferably includes for example SiH of silane 4, Si 2H 6With the hexamethyl disiloxane.
The additive of above-mentioned DLG or DLC film can be incorporated in quasi-diamond matrix or be attached to the surface atom layer.If described additive is incorporated in quasi-diamond matrix, it may cause density and/or structural disturbance, but resulting materials is the close-packed network with diamond-like carbon feature (for example unreactiveness, hardness and barrier properties) basically.If additive concentration too large (for example for carbon concentration higher than 50 atom %), density may be influenced and the beneficial property diamond-like carbon network will lose.If additive is attached to the surface atom layer, they can only change surface tissue and characteristic.The mass permanence of diamond-like carbon network is kept.
Plasma-deposited polymkeric substance such as quasi-diamond glass and diamond-like carbon can be from plasma body by using precursor monomer synthetic in low-temperature gaseous phase.The high-energy electron that precursor molecule is present in plasma body decomposes to form the free radical material.These free radical materials react and make polymeric film grow at substrate surface.Non-specific due to reaction process in described gas phase and described substrate is therefore the resulting polymers film is normally highly cross-linked and unbodied in nature.About the relevant Additional Information of plasma-deposited polymkeric substance, referring to for example H.Yasuda, " plasma polymerization effect (Plasma Polymerization), " academic publishing company (Academic Press Inc.), New York (New York) (1985); R.d ' Agostino (Ed), " plasma-deposited, the processing of polymkeric substance and etching (Plasma Deposition, Treatment ﹠amp; Etching of Polymers) Etching of Polymers) ", U.S. academic press, New York (1990)); And H.Biederman and Y.Osada, " Plasma Polymerization Processes " (plasma polymerization technique), Ace Wei Er (Elsever), New York (1992).
Usually, owing to having hydrocarbon and containing for example CH of carbon functional group 3, CH 2, CH, Si-C, Si-CH 3, Al-C, Si-O-CH 3Deng, therefore described plasma-deposited polymer layer has organic nature herein.Described plasma-deposited polymer layer is substantially substoichiometric on its inorganic component and is rich carbon substantially.For example in siliceous film, oxygen silicon ratio is usually less than 1.8 (silicon-dioxide has 2.0 ratio), and more generally lower than 1.5 (for DLG), and carbon content is at least approximately 10%.In certain embodiments, carbon content is at least approximately 20% or 25%.
As utilizing silicone oil and the optional silane source in order to form plasma body also to can be used in barrier film by the amorphous-type diamond film that ion strengthens plasma activated chemical vapour deposition (PECVD) formation described in U.S. Patent Application Publication 2008-0196664 (David etc.).Term " organosilicon ", " silicone oil " or " siloxanes " use interchangeably, refer to have structural unit R 2SiO oligomeric and the molecule of high molecular more, wherein R is independently selected from hydrogen, (C 1-C 8) alkyl, (C 5-C 18) aryl, (C 6-C 26) aralkyl or (C 6-C 26) alkaryl.These also can be known as organopolysiloxane and comprise silicon and Sauerstoffatom alternately (chain O-Si-O-Si-O-) often also has and the free valency Siliciumatom of R group joint, but also can engage (crosslinked) to Sauerstoffatom and the Siliciumatom of second chain, thereby form extended network (high molecular).In certain embodiments, so that being amount flexible and that have high optical transmittance, the coating that the gained plasma body forms introduces the silicone oil that silicone source is for example evaporated.The process gas that any other is available, for example oxygen, nitrogen and/or ammonia, can use to help to keep the character of plasma body and modification amorphous-type diamond rete together with siloxanes and the silane of choosing wantonly.
In certain embodiments, can use the combination of two or more different plasma-deposited polymkeric substance.For example, form different plasma-deposited polymer layers by changing or forming plasma body with the pulse mode feeding with the process gas of deposited polymer layer.And for example, can form the first layer of the first amorphous-type diamond film, then can form the second layer of the second amorphous-type diamond film on described the first layer, wherein said the first layer has different compositions from the described second layer.In certain embodiments, the first amorphous-type diamond rete is formed by the silicone oil plasma body, and then the second amorphous-type diamond rete is formed by silicone oil and silane plasma body.In other embodiments, formation replaces two or more amorphous-type diamond retes of composition to generate the amorphous-type diamond film.
Plasma-deposited polymkeric substance for example quasi-diamond glass and diamond-like carbon can have any available thickness.In certain embodiments, plasma-deposited polymkeric substance can have the thickness of at least 500 dusts or at least 1,000 dust.In certain embodiments, the thickness of plasma-deposited polymkeric substance can be in 1,000 to 50,000 dust, 1,000 to 25,000 dust or 1,000 to 10,000 dust scope.
Prepare available barrier film 120 for example other plasma deposition methods of rich carbon film, silicon-containing film or their combination have open in for example U.S. Patent number 6,348,237 people such as () Kohler.Rich carbon film can contain the carbon of at least 50 atom %, the carbon of common approximately 70-95 atom %, the nitrogen of 0.1-20 atom %, the hydrogen of the oxygen of 0.1-15 atom % and 0.1-40 atom %.Depend on its physics and chemistry character, so rich carbon film can be categorized as " amorphous ", " hydrogenation is amorphous ", " graphite ", " i-carbon " or " quasi-diamond ".Silicon-containing film is often silicon polymer-type and that contain any composition, carbon, hydrogen, oxygen and nitrogen.
Rich carbon film and silicon-containing film can be by plasma body and evaporation the interaction formation of organic materials, described organic materials is generally liquid under envrionment temperature and pressure.The organic materials of described evaporation can condense in the vacuum lower than approximately 1 holder (130Pa) usually.Described for plasma polymer deposition as mentioned, at electronegative electrode place, (for example, in conventional vacuum chamber) in a vacuum, with steam towards flexibility, the guiding of visible light transmissive base material.Allow organic materials interaction during film forms of plasma body (for example, argon plasma or rich carbon plasma are as U.S. Patent No. 5,464, described in 667 people such as () Kohler) and at least a vaporization.Plasma body is the plasma body that can activate the organic materials of evaporation.The organic materials of plasma body and evaporation can interact on the surface of substrate or with the Surface Contact of substrate before interact.Which kind of mode no matter, the organic materials of evaporation and the interaction of plasma body provide the reactive form (for example, methyl loses) of organic materials from organosilicon so that material when forming film due to for example polymerization and/or crosslinked and can densification.Importantly, the preparation of described film does not need solvent.
The film that forms can be uniform multi-component membranes (for example, by one deck coating of multiple parent material production), single component film and/or multilayer film (for example, the alternating layer of carbon-rich material and organosilicon material) uniformly.For example, use once may form the multi-ply construction (for example layer of the dimethyl siloxane of the layer of carbon-rich material, at least part of polymerization and centre or the interfacial layer of carbon/dimethyl siloxane matrix material) of film from the rich carbon plasma in a stream in the first source with from the high molecular organic liquid (for example dimethicone oils) of evaporation in another stream in the second source by the deposition program.The change of System Construction makes uniform multi-component membranes or layered membrane controllably form, as required, and gradual change or the sudden change on character and composition of described film.A kind of uniform coating of material also can be formed by high molecular organic liquid (for example dimethicone oils) the carrier gas plasma body of for example argon gas and evaporation.
Other available barrier films comprise having the film that gradient forms barrier coat, for example at U.S. Patent number 7,015, and those described in 640 people such as () Schaepkens.Film with gradient composition barrier coat can make by reaction or the recombinant products of deposition reaction material on the polymeric film base material.Thereby change the relative supply rate of reactive material or the kind of change reactive material and obtain having at whole thickness the coating that gradient forms.The coating composition that is fit to is organic and inorganic or stupalith.These materials normally the react reaction of plasma species or recombinant products and be deposited on substrate surface.Organic-containing materials comprises carbon, hydrogen, oxygen and optional other trace element usually, such as sulphur, nitrogen, silicon etc., and this depends on the type of reactant.The suitable reactant that produces organic composite in coating is to have straight or branched alkane up to 15 carbon atoms, alkene, alkynes, alcohol, aldehyde, ether, oxirane, aromatic hydrocarbons etc.Inorganic and ceramic coating material generally includes oxide compound; Nitride; Carbide; Boride; The perhaps combination of IIA, IIIA, IVA, VA, VIA, VIIA, IB and IIB family element; The metal of IIIB, IVB and VB family; And rare earth metal.For example, can pass through by silane (SiH 4) and the plasma body restructuring that produces of for example methane or dimethylbenzene organic materials silicon carbide is deposited on base material.Can be by the plasma-deposited silicon oxide carbide by silane, methane and oxygen or silane and propylene oxide generation.The plasma-deposited silicon oxide carbide that also can produce by the organosilicon precursor by for example tetraethoxysilane (TEOS), hexamethyldisiloxane (HMDSO), hexamethyldisilazane (HMDSN) or octamethylcyclotetrasiloxane (D4).Can be by the plasma-deposited silicon nitride that is produced by silane and ammonia.The plasma-deposited oxygen carbon aluminium nitride that can produce by the mixture by tartrate aluminium and ammonia.Other that can the selective reaction thing makes up to obtain required coating composition.The selection of concrete reactant belongs to those skilled in the art's technical ability.Can pass through to put into the composition of the reactant of reactor chamber with the formation coating or by for example overlapping deposition region of use in web technique in change between the reaction product depositional stage, thereby the gradient of acquisition coating forms.Can form coating by a kind of in many kinds of deposition techniques or their combination, for example plasma enhanced chemical vapor deposition (PECVD), radio-frequency plasma strengthen chemical vapour deposition (RFPECVD), swelling heat-plasma activated chemical vapour deposition (ETPCVD), the sputter that comprises reactive sputtering, electron cyclotron resonace-plasma enhanced chemical vapor deposition (ECRPECVD), inductively coupled plasma and strengthen chemical vapour deposition (ICPECVD).Coat-thickness usually at about 10nm in about 10000nm scope, in certain embodiments, for about 10nm to about 1000nm, in certain embodiments, for about 10nm to about 200nm.Record along normal axis, barrier film is at least approximately 75% (be at least in certain embodiments, approximately 80,85,90,92,95,97 or 98%) to the average transmittance on the visible part of spectrum.In certain embodiments, barrier film is at least about 75% (in certain embodiments, at least about 80%, 85%, 90%, 92%, 95%, 97% or 98%) to 400nm to the average transmittance on the 800nm scope.
Other suitable barrier films comprise the thin and flexible glass that is laminated on polymeric film and the glass that is deposited on polymeric film.
Referring to Figure 10, exemplary transparent configuration surface film 100 comprises structured film base material 102, and structured film base material 102 has the main structure face, and the main structure face has the textured surface of the form that is the prism rib.Each textured surface has the tip angle κ less than 90 degree.Film 100 also has textured surface 102 from the basic component 103 of its extension.Structured surface 102 also is coated with the layer of porous silicon dioxide nano particle 101, and porous silicon dioxide nano particle 101 can be sintered.Supporting backing 103 can be for example transparent polymer materials.exemplary polymer materials can comprise poly-(methyl) methyl acrylate (PMMA) film, poly(vinylidene fluoride) (PVDF) film, the PMMA/PVDF/UVA blend membrane, polyethylene terephthalate (PET) film, scribble the PET film of priming paint, polycarbonate membrane, three strata carbonic ether films with PMMA/PVDF/UVA blend top layer, crosslinked polyurethane film, acrylate films, at least one in ethylene fluoride-propylene (FEP) film or UV mirror film or combination.The binder layer 104 of optically clear and textured surface face 102 are opposing and be used for the adhesion arrangement surface film to the dimensional stabilizing film 105 that is coated with oxide compound barrier coat 106.Exemplary dimensional stabilizing film comprises thermally stable P ET and UV mirror.
Referring to Figure 11, exemplary flexible photovoltaic module 110 comprises structured film base material 112, and structured film base material 112 has the main structure face, and the main structure face has the textured surface of the form that is the prism rib.Each textured surface has the tip angle σ less than 90 degree.Film 110 also has textured surface 112 from the basic component 113 of its extension.Structured surface 112 also is coated with the layer of porous silicon dioxide nano particle 111, and porous silicon dioxide nano particle 111 can be sintered.Supporting backing 113 can be for example transparent polymer materials.exemplary polymer materials can comprise poly-(methyl) methyl acrylate (PMMA) film, poly(vinylidene fluoride) (PVDF) film, the PMMA/PVDF/UVA blend membrane, polyethylene terephthalate (PET) film, scribble the PET film of priming paint, polycarbonate membrane, three strata carbonic ether films with PMMA/PVDF/UVA blend top layer, crosslinked polyurethane film, acrylate films, at least one in ethylene fluoride-propylene (FEP) film or UV mirror film or combination.The binder layer 114 of optically clear and textured surface face 112 are opposing and be used for the adhesion arrangement surface film to the dimensional stabilizing film 105 that is coated with oxide compound barrier coat 116.Exemplary dimensional stabilizing film comprises thermally stable P ET and UV mirror.Exemplary structured surface film is laminated to CIGS photovoltaic cell 118 with packaged material 117.Another blocking layer 119 is opposing with structured surface film, and this blocking layer can be tinsel or the barrier oxide layers coated film on flexible photovoltaic module dorsal part.
Can be with some embodiment and the moisture barrier combination of goods described herein, wherein the structurizing base material also comprises the backing face, moisture barrier (can for example derive from (the 3M Company of 3M company in Sao Paulo, the Minnesota State with for example tackiness agent of optically clear with trade(brand)name " OCA8172 ", St.Paul, MN)) be bonded to the backing face of structurizing base material.The textured surface anti-reflective film can be by adding UVA (can for example derive from the Ciba company (Ciba Specialty Chemicals, Tarrytown, NY) of New York Ta Lidun with trade(brand)name " TINUVIN 1577 ") and modification to skin.The flexible PET film that the surface structuration anti-reflective film with UV absorption agent can be laminated to the alternating layer that has been coated with sieve and silica-sesquioxide and acrylic ester polymer on one surface (can for example derive from (the Dupont Teijin Films of Supreme Being people's film company of Du Pont of Wilmington, the Delaware State with trade(brand)name " ST-505 ", Wilmington, DE)) opposing surface.
Exemplary flexible solar battery or solar energy module can for example use the front side barrier film manufacturing of textured surface antireflection.Surface tissue anti-reflective film structure and flexible solar battery or the flexible battery string of coating Nano particles of silicon dioxide can be laminated together, have the reflection of enhancing inhibition and ultralow (under 50 ℃ less than 0.005g/m to make 2) the flexible battery/module of water vapor transmission rate (WVTR).Aluminium foil the first layer with the optional dielectric layer that is bonded on its top surface can be tiled on the laminated instrument of vacuum.Can lay one deck packaged material on the surface of aluminium foil, when being heated to the temperature of appointment, described packaged material is with melting and mobile.Can lay the string of flexible solar battery or flexible solar battery on encapsulants and aluminium foil layer.Can lay another layer encapsulants on solar cell/battery strings.In the end lay Nano particles of silicon dioxide textured surface reflectance coating on one deck encapsulants at last.Can be by closed vacuum laminator, heat and time that the atmosphere of the laminator of finding time reaches appointment is laminated to all layers in flexible solar battery or module together.Result obtains flexible solar battery or solar energy module.
The solar photovoltaic module is known in the art, in the situation of rigidity photovoltaic module (for example, the crystalline silicon module), usually has glass front.For the flexible photovoltaic module that adopts thin film technique, the front surface base material is generally the stable polymeric film of UV (for example ethylene-tetrafluoroethylene).Some embodiment of goods described herein can be used in luminous energy or solar heat absorption unit.For example, the luminous energy absorption unit can comprise the light absorber with luminous energy receiving plane; And be arranged so that between the source and luminous energy receiving plane of luminous energy, simultaneously from the luminous energy in described source by goods described herein that light absorber absorbed.Exemplary absorption means comprises: comprise the photovoltaic devices of the photovoltaic cell that can be wound at least one volume or folding and not impaired (for example, battery cracking or battery strings electrical short), and the rigidity photovoltaic devices.Goods described herein on the first major surfaces that a kind of exemplary solar heat heating unit comprises heat absorber with first major surfaces, be arranged in heat absorber and be arranged in the first major surfaces of heat absorber inside or heat absorber and described goods between in one of at least in liquid or gas.The solar heat absorbing material is chosen as and effectively absorbs sun power and usually have low emissivity coatings so that radiant heat energy no longer.
The solar thermal energy module is known in the art, and it is trap thermal energy by collecting sun power and heating fluid.The similarity of solar heat module and photovoltaic module be its normally rigidity and have glass front, described glass front has at least one surface reflection and the trend of trapped dirt is arranged.The capture that textured surface anti-reflective film described herein can reflect by minimum surface, especially the surface reflection under higher incident angle of light promotes more energy.Nano particles of silicon dioxide coating on textured surface anti-reflective film described herein can attract to capture more energy by minimizing dirt; Increasing the light transmission advances the total transmittance in the solar heat resorber and therefore improves its efficient.
In certain embodiments, the Nano particles of silicon dioxide coating can be applied on the spot photovoltaic module or the anti-reflection structureization on the solar heat panel surface of operation.In certain embodiments, the method comprise on the spot the operation photovoltaic module or the front surface of solar heat panel apply the anti-reflection structure surface film that has been coated with Nano particles of silicon dioxide.Lose validity if the Nano particles of silicon dioxide coating is in operation because of abrasion (for example, wearing and tearing), apply the Nano particles of silicon dioxide coating on the textured surface on the spot and will recover for example to refuse dirt.
Exemplary embodiment
1. goods, described goods comprise transparent substrate with anti-reflection structure surface and the sinter fuse coating of the porous network that comprises Nano particles of silicon dioxide on it, and wherein said Nano particles of silicon dioxide is bonded to adjacent Nano particles of silicon dioxide.
2. goods described according to embodiment 1, the porous network of wherein said Nano particles of silicon dioxide is three-dimensional network.
3. goods described according to embodiment 1 or 2, wherein said sinter fuse coating is conformal coating with respect to the anti-reflection structureization surface of transparent substrate.
4. goods described according to any one in previous embodiment, wherein said nanoparticle has bimodal distribution of sizes.
5. goods described according to any one in previous embodiment, the median size of wherein said nanoparticle is 400 nanometers at the most.
6. goods described according to any one in previous embodiment, the median size of wherein said nanoparticle is 300 nanometers at the most.
7. goods described according to any one in previous embodiment, the median size of wherein said nanoparticle is 200 nanometers at the most.
8. goods described according to any one in previous embodiment, the median size of wherein said nanoparticle is 150 nanometers at the most.
9. goods described according to any one in previous embodiment, the median size of wherein said nanoparticle is 100 nanometers at the most.
10. goods described according to any one in previous embodiment, the median size of wherein said nanoparticle is 75 nanometers at the most.
11. goods described according to any one in previous embodiment, the median size of wherein said nanoparticle is 50 nanometers at the most.
12. goods described according to any one in previous embodiment, the median size of wherein said nanoparticle is 40 nanometers at the most.
13. goods described according to any one in previous embodiment, the median size of wherein said nanoparticle is 30 nanometers at the most.
14. goods described according to any one in previous embodiment, the median size of wherein said nanoparticle is 20 nanometers at the most.
15. goods described according to any one in previous embodiment, wherein said nanoparticle has bimodal distribution.
16. goods described according to embodiment 15, first of the bimodal distribution of wherein said nanoparticle are distributed in 2 nanometer to 15 nanometer range, second be distributed in 20 nanometer to 500 nanometer range.
17. goods described according to embodiment 15, first of the bimodal distribution of wherein said nanoparticle are distributed in 2 nanometer to 20 nanometer range, second be distributed in 30 nanometer to 500 nanometer range.
18. goods described according to embodiment 15, first of the bimodal distribution of wherein said nanoparticle are distributed in 5 nanometer to 15 nanometer range, second be distributed in 20 nanometer to 100 nanometer range.
19. goods described according to any one in embodiment 15-17, the weight ratio of wherein said the first relatively described the second distribution nanoparticle of distribution nanoparticle is in 1: 99 to 99: 1 scope.
20. goods described according to any one in embodiment 15-17, the weight ratio of wherein said the first relatively described the second distribution nanoparticle of distribution nanoparticle is in 10: 90 to 90: 10 scopes.
21. goods described according to any one in embodiment 15-17, the weight ratio of wherein said the first relatively described the second distribution nanoparticle of distribution nanoparticle is in 20: 80 to 80: 20 scopes.
22. goods described according to any one in embodiment 15-17, the weight ratio of wherein said the first relatively described the second distribution nanoparticle of distribution nanoparticle is in 30: 70 to 70: 30 scopes.
23. goods described according to any one in previous embodiment, wherein said textured surface are microstructured surface.
24. goods described according to any one in previous embodiment, wherein said surface tissue comprises prism.
25. goods described according to embodiment 24, wherein said prism respectively be included in 15 degree to the 75 degree scopes the prism tip angle and at 10 microns the pitch to 250 micrometer ranges.
26. goods described according to embodiment 24, wherein said prism respectively be included in 15 degree to the 75 degree scopes mean obliquity and at 10 microns the pitch to 250 micrometer ranges.
27. goods described according to any one in embodiment 24-26, the paddy-peak heights of wherein said prism at 10 microns to 250 micrometer ranges.
28. goods described according to any one in previous embodiment, wherein said surface tissue has peak and paddy and average peak-to-valley height, wherein said sinter fuse coating has mean thickness, and the mean thickness of wherein said sinter fuse coating is at most described average peak-to-valley height half.
29. according to the described goods of any one in embodiment 1-27, wherein said surface tissue has peak and paddy and average peak-to-valley height, wherein said sinter fuse coating has mean thickness, and the mean thickness of wherein said sinter fuse coating is lower than 25% of described average peak-to-valley height.
30. goods described according to any one in previous embodiment, wherein said sinter fuse coating is conformal coating with respect to the anti-reflection structureization surface of transparent substrate.
31. goods described according to any one in previous embodiment, wherein said sinter fuse coating specific surface structure is from have higher optical transmittance on wider incident angle of light scope.
32. goods described according to any one in previous embodiment, wherein said transparent substrate are film.
33. having vertical and wherein said surface tissue, goods described according to embodiment 32, wherein said film comprise the prism with the linear grooves longitudinally that is parallel to transparent film.
34. goods described according to embodiment 32 or 33, the anti-reflection structure surface of wherein said transparent film has the structured surface of anti-luminous reflectance, and wherein described at least anti-reflection structure comprises polymer materials.
35. goods described according to embodiment 32 or 33, wherein said anti-reflection structure surface transparent film comprises static dissipative material.
36. goods described according to embodiment 32 or 33, the anti-reflection structure surface of wherein said transparent film has the structured surface of anti-luminous reflectance, and wherein described at least anti-reflection structure comprises crosslinked polymer materials.
37. goods described according to embodiment 32 or 33, the anti-reflection structure surface of wherein said transparent film has the structured surface of anti-luminous reflectance, wherein described at least anti-reflection structure comprises crosslinked polymer materials, and the cross-linked polymer density of wherein said textured surface is higher than the rest part of film.
38. goods described according to embodiment 37, wherein said textured surface have the crosslinked polymer density higher than the rest part of described anti-reflection structure film.
39. goods described according to embodiment 37 or 38, wherein the crosslinked polymer density of the core segment of each described structure is lower than the crosslinked polymer density of described textured surface.
40. goods described according to any one in embodiment 37-39, wherein said film comprises that also described structure is from the basic component of its extension, all polymer elastomer materials of each described structure all have the crosslinked polymer density approximately same high with described textured surface, and the crosslinked polymer density of described basic component is lower than the crosslinked polymer density of each described structure.
41. goods described according to embodiment 32-40, the optical transmittance of wherein said film after described textured surface experience staining test changes less than 8%.
42. goods described according to embodiment 32-41, the optical transmittance of wherein said film after the sand trial of described textured surface experience changes less than 8%.
43. the goods described according to any one in previous embodiment with the transparent supporting backing combination with interarea, wherein said transparent supporting backing dissipation static, and described structurizing base material comprises that also the backing face of the interarea that is bonded to described supporting backing is to form the anti-reflection structure goods that strengthen.
44. a luminous energy absorption unit, it comprises:
Light absorber with luminous energy receiving plane; With
According to the described goods of any one in embodiment 1 to 42, described goods are arranged so that between the source and described luminous energy receiving plane of luminous energy, and the luminous energy from described source is absorbed by described light absorber simultaneously.
45. device described according to embodiment 44, wherein said absorption means are to comprise the photovoltaic devices that can be wound at least one volume or folding and not impaired photovoltaic cell.
46. device described according to embodiment 45, wherein said absorption means are the rigidity photovoltaic devices.
47. a solar heat heating unit, it comprises:
Heat absorber with first major surfaces;
According to the described goods of any one in embodiment 1 to 42, described goods are arranged on the first major surfaces of described heat absorber; With
During liquid, described liquid are arranged between the first major surfaces of the inner or described heat absorber of described heat absorber and described goods one of at least.
48. a method for preparing goods, described method comprises:
Apply on the anti-reflection structure surface of transparent substrate comprise Nano particles of silicon dioxide coating composition so that coating to be provided; With
Heat described coating to provide according to the described goods of any one in embodiment 1 to 42.
49. method described according to embodiment 48 wherein applies described coating composition and comprises the use air knife.
50. method described according to embodiment 48 or 49, before it also was included in and applies coating composition to transparent substrate, the anti-reflection structureization of the described transparent substrate of corona treatment was surperficial.
51. according to the described method of any one in embodiment 48 to 50, the pH of wherein said coating composition is less than 5.
52. according to the described method of any one in embodiment 48 to 50, the pH of wherein said coating composition is less than 4.
53. according to the described method of any one in embodiment 48 to 50, the pH of wherein said coating composition is less than 3.
54. according to the described method of any one in embodiment 48 to 53, wherein said coating composition is by merging at least aqueous dispersion and the pK that comprises Nano particles of silicon dioxide a＜3.5 acid and making.
55. method described according to embodiment 54, wherein said acid are at least a in following acid: oxalic acid, citric acid, H 3PO 4, HCl, HBr, HI, HBrO 3, HNO 3, HClO 4, H 2SO 4, CH 3SO 3H, CF 3SO 3H, CF 3CO 2H or CH 3SO 2OH.
56. according to the described method of any one in embodiment 48 to 55, wherein said coating composition is aqueous dispersion.
57. according to the described method of any one in embodiment 48 to 56, wherein said coating composition also comprises tetraalkoxysilane.
58. according to the described method of any one in embodiment 48 to 57, wherein said coating composition also comprises surfactant.
59. according to the described method of any one in embodiment 48 to 58, wherein said coating composition also comprises wetting agent.
60. a method for preparing goods, described method comprises:
Apply on the anti-reflection structure surface of transparent substrate comprise the core-shell silica nanoparticle coating composition so that coating to be provided, wherein each core-shell particles comprises polymer core, the shell that described polymer core is disposed in the atresia preparing spherical SiO 2 particles on polymer core holds, and the volume average particle size of wherein said atresia preparing spherical SiO 2 particles is not more than 60 nanometers; With
Heat described coating to provide according to the described goods of any one in embodiment 1 to 42.
61. method described according to embodiment 60 wherein applies described coating composition and comprises the use air knife.
62. method described according to embodiment 60 or 61, before it also was included in and applies coating composition to transparent substrate, the anti-reflection structureization of the described transparent substrate of corona treatment was surperficial.
63. according to the described method of any one in embodiment 60 to 62, the pH of wherein said coating composition is less than 5.
64. according to the described method of any one in embodiment 60 to 62, the pH of wherein said coating composition is less than 4.
65. according to the described method of any one in embodiment 60 to 62, the pH of wherein said coating composition is less than 3.
66. according to the described method of any one in embodiment 60 to 65, wherein said coating composition is by merging at least aqueous dispersion and the pK that comprises Nano particles of silicon dioxide a＜3.5 acid and making.
67. method described according to embodiment 66, wherein said acid are at least a in following acid: oxalic acid, citric acid, H 3PO 4, HCl, HBr, HI, HBrO 3, HNO 3, HClO 4, H 2SO 4, CH 3SO 3H, CF 3SO 3H, CF 3CO 2H or CH 3SO 2OH.
68. according to the described method of any one in embodiment 60 to 67, wherein said coating composition is aqueous dispersion.
69. according to the described method of any one in embodiment 60 to 68, wherein said coating composition also comprises tetraalkoxysilane.
70. according to the described method of any one in embodiment 60 to 69, wherein said coating composition also comprises surfactant.
71. according to the described method of any one in embodiment 60 to 70, wherein said coating composition also comprises wetting agent.
72. a method for preparing goods, described method comprises:
Apply on the anti-reflection structure surface of transparent substrate comprise Nano particles of silicon dioxide coating composition so that coating to be provided, the pH of wherein said coating composition is lower than 3; With
Make Nano particles of silicon dioxide acid sintering, to provide according to previous embodiment 1 to 42 described goods.
73. method described according to embodiment 72 wherein applies described coating composition and comprises the use air knife.
74. method described according to embodiment 72 or 73, before it also was included in and applies coating composition to transparent substrate, the anti-reflection structureization of the described transparent substrate of corona treatment was surperficial.
75. according to the described method of any one in embodiment 72 to 74, the pH of wherein said coating composition is less than 2.
76. according to the described method of any one in embodiment 72 to 74, the pH of wherein said coating composition is in 1.5 to 3 scopes.
77. according to the described method of any one in embodiment 72 to 76, wherein said coating composition is aqueous dispersion.
78. according to the described method of any one in embodiment 72 to 77, wherein said coating composition also comprises tetraalkoxysilane.
79. according to the described method of any one in embodiment 72 to 78, wherein said coating composition also comprises surfactant.
80. according to the described method of any one in embodiment 72 to 79, wherein said coating composition also comprises wetting agent.
Following example further illustrates advantage of the present invention and embodiment, but the concrete material of mentioning in these examples and amount and other conditions and details should not be interpreted as improper restriction of the present invention.Except as otherwise noted, otherwise all umbers and per-cent all by weight.
Example 1
little rf polymethylmethacrylate optics luminescent film (derives from the 3M company (3M Company, St.Paul.MN) in Sao Paulo, the Minnesota State before with trade(brand)name " OPTICAL LIGHTING FILM ", now for derive from the substitute products of 3M company (3M Company) with trade(brand)name " OPTICAL LIGHTING FILM 2301 ") be coated with by acidifying water-based nano-particle solution, described acidifying water-based nano-particle solution makes in the following way: mix the 70%20nm particle solution (with Ondeo Nalco Co. (the Nalco Company of trade(brand)name " NALCO 1050 NANOPARTICLE SOLUTION " available from uncle's Weir in the Illinois, Naperville, IL)) with 30%4nm Nano particles of silicon dioxide solution (with trade(brand)name " NALCO 1115 NANOPARTICLE SOLUTION " available from Ondeo Nalco Co. (Nalco Company)), the nitric acid of 3wt.% is added in this solution that can directly use, and is diluted to 5wt.% to obtain the approximately dry thickness of 20nm with deionized water.Then the acrylic acid or the like prismatic film of nano silicon coating is heated to 85 ℃ 1 hour.
With reference to Fig. 8, it is the camera digital picture of the cross section of the exemplary acids fused silica nanoparticle that is coated with on the anti-reflecting surface structure.Transparent configuration surface film base material 83 has textured surface prism 82, and prism 82 has the tip angle less than 90 degree
Figure BPA00001701421000571
The face of each prism is coated with the layer 81 of porous silica.
Stand (above-mentioned) staining test at sample and carry out before and afterwards transmissivity measurement.Before staining test, the transparent configuration surface film of nano silicon coating has 96% transmissivity, described transmissivity with spectrophotometer (with trade(brand)name " HAZE Gard PLUS " available from the Colombian Bi Ke in the Maryland State-Gartner (BYK-Gardner of company, Columbia, MD)) record.After standing staining test, transmissivity remains on 93%, has 3% transmission losses.By comparing, the little rf polymethylmethacrylate optics luminescent film (" 3M OPTICAL LIGHTING FILM ") that stands uncoated (namely without the nanometer titanium dioxide silicon coating) of staining test has 11% transmission losses.
Example 2
Make little polygram casting mould with 100 microns pitch cutting linear prism grooves with the diamond that drift angle is 53 degree on the copper roller.Then use the little casting roll mould that copies of this metal, by extrude continuously and the quenching melt polypropylene, produce " rib " the 53 degree linear prism polyacrylic polymer film dies with identical patterns on this metal casting roller mould.
Use the dull and stereotyped apparatus for coating of notch bar and following program to prepare polyurethane film.use the screw blade mixing machine to mix 1368 gram aliphatic polyester polyols (with Jin Shi industrial (the King Industries of trade(brand)name " K-FLEX 188 " available from Connecticut State Cécile Nowak, Norwalk, CT)) with 288 gram hydroxyphenyl-triazine UV light stabilizing agent (with Ciba company (the Ciba Specialty Chemicals of trade(brand)name " TINUVIN 405 " available from New York Ta Lidun, Tarrytown, NY)), 144 gram hindered amine as light stabilizer (with trade(brand)name " TINUVIN123 " available from Ciba company (Ciba Specialty Chemicals)) and 4.3 gram dibutyltin dilaurate catalysts are (with air Chemicals company limited (the Air Products and Chemicals Inc. of trade(brand)name " DABCO T12 " available from Pennsylvania Alan town, Allentown.PA)) approximately 10 minutes.With in the vacuum drying oven of this polyol blends under 60 ℃ degassed 15 hours, in the section's distribution drum of then packing plastics A into conventional and insulation under 50 ℃ in baking oven.Hexamethylene diisocyanate (with the Bayer MaterialScience AG company (Bayer Materials Sciences.Pittsburg.PA) of trade(brand)name " DESMODUR N3300A " available from the Pennsylvania Pittsburgh) is packed in B section distribution drum, also insulation under 50 ℃.Conventional variable drive pump is set, and making the volume ratio of A section and B section is 100: 77.Used the long described two kinds of components of static mixer fusion of 300mm (12 inches) before coating.With the polymetylmethacrylate film (with Arkema (the Arkema Inc. of trade(brand)name " SOLARKOTE " available from philadelphia, pa, Philadelphia, PA)) be loaded on lower unwinding device, and polypropylene rib mold membrane is loaded on upper unwinding device.Linear velocity with 5 feet per minute clocks (1.5m/min) is coated with described film.The platen baking oven that is heated has 5 zones, long 4 feet (1.2m) in each zone.Be 160 ℉ (71 ℃) with the Temperature Setting in front 4 zones, and last zone is set as room temperature.The winding tension of the film of the unwinding tension of top and bottom liner and gained coating all is set to 20 pounds (89N).Gap between roll gap two, the place liner that is formed by notch bar and platform is set to 3 mils (0.075mm).After applied and coiling, before assessment, it is at room temperature regulated at least 3 days at film.After curing, produce " rib " micro-structural cross-linked polyurethane thereby remove the polypropylene molds film on the PMMA film.
Then with the little rf urethane prism of acidifying water-based nano-particle solution coating, described acidifying water-based nanoparticle makes in the following way: mix 70%20nm particle solution (" NALCO 1050 NANOPARTICLE SOLUTION ") and 30%4nm Nano particles of silicon dioxide solution (" NALCO 1115 NANOPARTICLE SOLUTION "); The nitric acid of 3wt.% is added in this solution that can directly use, and is diluted to 5wt.% to obtain the approximately dry thickness of 20nm with deionized water.Then the acrylic acid or the like prismatic film with the nano silicon coating was heated to 85C 1 hour.
Stand (above-mentioned) staining test at sample and carry out before and afterwards transmissivity measurement.Before staining test, the urethane prism of the nano silicon coating on the PMMA film has 97% transmissivity, and described transmissivity uses spectrophotometer (" HAZE GARD PLUS ") to record.After standing staining test, transmissivity remains on 94%, has 3% transmission losses.By comparing, the urethane prism that stands uncoated (namely without the nanometer titanium dioxide silicon coating) on the PMMA film of staining test has 15% transmission losses.
Example 3
use the blend of the polycarbonate (with trade(brand)name " MAKROLON OD2015 " available from company of Bayer MaterialScience AG (Bayer Materials Science)) of 90wt% and the PC-UVA masterbatch of 10wt% (with trade(brand)name " SUKANO TA28-09 MB01 " available from Sukano Polymer Company (Sukano Polymers Corporation)) (" PC-UVA ") as the polymethylmethacrylate (" PMMA " of sandwich layer and 65wt.%, " CP-82 ") blend of polyvinylidene (with trade(brand)name " PVDF 6008 " available from Da Niang company (Dyneon)) of (it contains the triazine ultraviolet absorber (with trade(brand)name " TINUVIN 1577 " available from Ciba company (Ciba Specialty Chemicals)) of 3wt.%) and 35wt.% is as the top layer, utilize 3 manifold moulds with polycarbonate trilamellar membrane and the poly(vinylidene fluoride) (Da Niang (Dyneon of company that reaches available from Minnesota State Losec with trade(brand)name " PVDF 6008 ", Oakdale, MN))/polymethylmethacrylate (with trade(brand)name " PMMA CP82 " available from Arkema (Arkema Inc.))/uv-absorbing masterbatch is (with (the Sukano Polymers Corporation of Sukano Polymer Company of trade(brand)name " SUKANO TA11-10 MB03 " available from South Carolina Duncan, Duncan, SC)) blend top layer coextrusion.Described sandwich layer is that 100 microns (4 mils) are thick, and PVDF/PMMA/UVA blend top layer is that 50 microns (2 mils) are thick.Then be coated with the stable polycarbonate trilamellar membrane of this UV with little rf urethane prism, afterwards as coating Nano particles of silicon dioxide as described in above example 2.
Stand (above-mentioned) staining test at sample and carry out before and afterwards transmissivity measurement.Before staining test, the urethane prism of the nano silicon coating on three strata carbonic ether films has 97.5% transmissivity, and described transmissivity uses spectrophotometer (" HAZE GARD PLUS ") to record.After standing staining test, transmissivity remains on 94.5%, has 3% transmission losses.By comparing, the uncoated urethane prism on this trilamellar membrane that stands staining test has 12% transmission losses.
Example 4
Use 90wt.% Polycarbonate ("MAKROLON? OD2015") and 10wt.% Of PC-UVA masterbatch (trade name "SUKANO? TA28-09? MB01" Sukano Polymers obtained from (Sukano? Polymers? Corporation )) as the core layer blend and 85wt.% polycarbonate ("MAKROLON? OD2015") and 10wt.% PC-UVA masterbatch ("SUKANO? TA28-09? MB01") and 5wt.% polymer antistatic additives (tradename "FC4400" available from 3M Company (3M? Company)) was used as a blend surface, using a 3-manifold die with a polycarbonate layer film of polycarbonate / FC4400 antistatic blend coextruded surface.Polycarbonate UVA blend sandwich layer is extruded to be poured into 100 microns (4 mils) thick, and PC/UVA/FC4400 blend top layer is that 50 microns (2 mils) are thick.Then use the stable polycarbonate sandwich layer of polyurethane coated this UV of little rf, be coated with Nano particles of silicon dioxide as described in above example 2 afterwards.
Before standing staining test and carry out afterwards transmissivity measurement.Before staining test, sample has 98% transmissivity, and described transmissivity uses spectrophotometer (" HAZE GARD PLUS ") to record.After standing staining test, transmissivity remains on 97%, has 1% transmission losses.By comparing, the uncoated urethane prism on identical polycarbonate trilamellar membrane that stands staining test has 4% transmission losses.
Example 5
PVDF/PMMA (80: 20) textured surface trilamellar membrane makes in the following way: the poly(vinylidene fluoride) of the 53 degree prism polymers mold membrane coextrusion 80wt.% that recline is (with Su Wei Plastics Company (the Solvay Plastics of trade(brand)name " PVDF 1008 " available from the Houston, Texas, Houston, TX))) and the polymethylmethacrylate of 20wt.% (with ICI acrylic acid or the like company (the ICI Acrylics Inc. of trade(brand)name " CP41 " available from St. Louis, the Missouri State, St.Louis, MO)) layer A, and while and middle PVDF/PMMA (20: 80) tack coat B and the 3rd coextrusion layer C coextrusion, in the middle of described PVDF/PMMA (20: 80) tack coat B by the poly(vinylidene fluoride) of 20wt% (with Su Wei Plastics Company (the Solvay Plastics of trade(brand)name " PVDF 1008 " available from the Houston, Texas, Houston, TX)) and the polymethylmethacrylate of 80wt% (with trade(brand)name " CP41 " available from ICI acrylic acid or the like company (ICI Acrylics Inc.)) make, described the 3rd coextrusion layer C by urethane (with Morton International, Inc. (the Morton International of trade(brand)name " MORTHANE PN03-215 " available from state of New Hampshire tin Brooker, Seabrook, NH)) make.The layer A of trilamellar membrane is cast into 19 micron thickness, and layer B is cast into 6 micron thickness, and layer C is cast into 69 micron thickness.After the removing polymer mold membrane, with the little rf PVDF/PMMA prism of acidifying water-based nano-particle solution coating, described acidifying water-based nanoparticle makes in the following way: mix 70%20nm particle solution (" NALCO 1050 NANOPARTICLE SOLUTION ") and 30%4nm Nano particles of silicon dioxide solution (" NALCO 1115 NANOPARTICLE SOLUTION ") subsequently; The nitric acid of 3wt.% is added in this solution that can directly use, and is diluted to 5wt.% to obtain the approximately dry thickness of 20nm with deionized water.Then the PVDF/PMMA prism of the Nano particles of silicon dioxide on polyurethane film coating is heated to 85 ℃ 1 hour.
Before standing staining test and carry out afterwards transmissivity measurement.Before staining test, sample has 98% transmissivity, and described transmissivity uses spectrophotometer (" HAZE GARD PLUS ") to record.After standing staining test, transmissivity remains on 96%, has 2% transmission losses.By comparing, the uncoated PVDF/PMMA blend prism on the polyurethane film sample that stands staining test has 11% transmission losses.
Example 6
the optics luminescent film (" OPTICAL LIGHTING FILM 2301 ") that makes by extruding little rf polycarbonate with acidifying aqueous urethane core-core/shell nanoparticles solution coat, and be dried to the approximately conformal thickness of 20nm on the optics luminescent film, described acidifying aqueous urethane core-core/shell nanoparticles solution is by mixing 2.5wt% Nano particles of silicon dioxide (with trade(brand)name " NALCO 2327 " available from Ondeo Nalco Co. (Nalco Company)) and 2.5wt.% polyurethane rubber latex (" NEOREZ A612 "), 3wt.% nitric acid in deionized water is 2.5 to make to pH.Then the acrylic acid or the like prismatic film of Nano particles of silicon dioxide coating is heated to 85 ℃ 1 hour.
Before standing staining test and carry out afterwards transmissivity measurement.Before staining test, sample has 98% transmissivity, and described transmissivity uses spectrophotometer (" HAZE GARD PLUS ") to record.After standing staining test, transmissivity remains on 96%, has 2% transmission losses.By comparing, the uncoated sample that stands staining test has 9% transmission losses.
Example 7
with anti-reflection structureization on PMMA film the surface-crosslinked carbamate prism of acidifying aqueous urethane core-core/shell nanoparticles solution coat as making as described in example 2, and be dried to the approximately conformal thickness of 20nm on structured surface film, described acidifying aqueous urethane core-core/shell nanoparticles solution is by mixing 4.5wt% Nano particles of silicon dioxide solution (with trade(brand)name " NALCO 1050 " available from Ondeo Nalco Co. (NALCO Company)) and 4.5wt% polyurethane rubber latex (with trade(brand)name " NEOREZ R960 " available from DSM profit health resin (the DSM Neoresins of company, Inc.), the pH of the nitric acid to 2.5 of 3wt.% in deionized water and making.Then the prismatic film of nano silicon polyurethane adhesive coating is heated to 85 ℃ 1 hour.
Before standing staining test and carry out afterwards transmissivity measurement.Before standing staining test, the crosslinked carbamate prism sheet material of nano silicon coating has 98% transmissivity, and described transmissivity uses spectrophotometer (" HAZE GARD PLUS ") to record.After standing staining test, transmissivity remains on 96%, has 2% transmission losses.By comparing, the uncoated crosslinked carbamate prismatic film that stands staining test has 9% transmission losses.
Example 8
Anti-reflection structureization surface PVDF/PMMA blend prismatic film can be similar to example 5 and make, different is polyurethane thermoplastic plastics (" MORTHANE PN03-215 ") base material by electrostatic dissipation polyurethane thermoplastic plastics (with trade(brand)name " STATRITE 5091 " available from (the Lubrizol Corporation of Ohioan Lubrizol Corp., Wickcliffe, OH)) replace.
Transmissivity measurement can carry out before standing staining test and on sample afterwards.Before staining test, sample has 98% transmissivity, and described transmissivity uses spectrophotometer (" HAZE GARD PLUS ") to record.After standing staining test, transmissivity remains on 97%, has 1% transmission losses.By comparing, the uncoated sample that stands staining test has 4% transmission losses.
Under the prerequisite that does not depart from the scope of the present invention with spirit, can make foreseeable modification and change to the present invention, this will be apparent to one skilled in the art.The present invention should not be subject to the embodiment that illustrates in order schematically to illustrate in present patent application.

Claims (10)

1. goods, described goods comprise transparent substrate with anti-reflection structure surface and the sinter fuse coating of the porous network that comprises Nano particles of silicon dioxide on it, and wherein said Nano particles of silicon dioxide is bonded to adjacent Nano particles of silicon dioxide.
2. goods according to claim 1, the porous network of wherein said Nano particles of silicon dioxide is three-dimensional network.
3. goods according to claim 1 and 2, wherein said sinter fuse coating is conformal coating with respect to the described anti-reflection structureization surface of transparent substrate.
4. according to the described goods of any one in aforementioned claim, wherein said nanoparticle has bimodal distribution of sizes.
5. according to the described goods of any one in aforementioned claim, wherein said sinter fuse coating is conformal coating with respect to the described anti-reflection structureization surface of transparent substrate.
6. according to the described goods of any one in aforementioned claim, wherein said sinter fuse coating has higher optical transmittance certainly than described surface tissue on wider incident angle of light scope.
7. according to the described goods of any one in aforementioned claim, wherein said transparent substrate is film.
8. goods according to claim 7, wherein said anti-reflection structure surface transparent film comprises static dissipative material.
9. goods according to claim 7, the described anti-reflection structure surface of wherein said transparent film has the structured surface of anti-luminous reflectance, wherein described at least anti-reflection structure comprises crosslinked polymer materials, and the cross-linked polymer density of wherein said textured surface is higher than the rest part of described film.
10. luminous energy absorption unit, it comprises:
Light absorber with luminous energy receiving plane; With
According to the described goods of any one in aforementioned claim, described goods are arranged as between the source of luminous energy and described luminous energy receiving plane, and the luminous energy from described source is absorbed by described light absorber simultaneously.
CN201180048399.5A 2010-10-06 2011-08-31 There is the antireflective article of the silica-based coating of nanometer titanium dioxide Expired - Fee Related CN103154320B (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US39052410P 2010-10-06 2010-10-06
US61/390,524 2010-10-06
PCT/US2011/049854 WO2012047422A1 (en) 2010-10-06 2011-08-31 Anti-reflective articles with nanosilica-based coatings

Publications (2)

Publication Number Publication Date
CN103154320A true CN103154320A (en) 2013-06-12
CN103154320B CN103154320B (en) 2015-12-16

Family

ID=44675818

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201180048399.5A Expired - Fee Related CN103154320B (en) 2010-10-06 2011-08-31 There is the antireflective article of the silica-based coating of nanometer titanium dioxide

Country Status (7)

Country Link
US (3) US20130186466A1 (en)
EP (1) EP2625313B1 (en)
JP (1) JP5869581B2 (en)
KR (3) KR102115937B1 (en)
CN (1) CN103154320B (en)
BR (1) BR112013008304A2 (en)
WO (1) WO2012047422A1 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106132519A (en) * 2014-04-11 2016-11-16 3M创新有限公司 Microporous article of interconnection Nano particles of silicon dioxide three-dimensional porous network with acid sintering and preparation method thereof
WO2017107783A1 (en) * 2015-12-25 2017-06-29 中国科学院上海高等研究院 Self-cleaning reflection reduction film and method of preparing same
CN107170852A (en) * 2017-06-27 2017-09-15 深圳市上古光电有限公司 A kind of light-weight solar component and its manufacture method

Families Citing this family (39)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9376593B2 (en) 2009-04-30 2016-06-28 Enki Technology, Inc. Multi-layer coatings
US9353268B2 (en) 2009-04-30 2016-05-31 Enki Technology, Inc. Anti-reflective and anti-soiling coatings for self-cleaning properties
WO2011139573A2 (en) 2010-04-28 2011-11-10 3M Innovative Properties Company Silicone-based material
KR20130096161A (en) 2010-04-28 2013-08-29 쓰리엠 이노베이티브 프로퍼티즈 컴파니 Articles including nanosilica-based primers for polymer coatings and methods
US9285584B2 (en) * 2010-10-06 2016-03-15 3M Innovative Properties Company Anti-reflective articles with nanosilica-based coatings and barrier layer
TW201333393A (en) * 2012-02-13 2013-08-16 Ind Tech Res Inst Apparatus for solar thermal collection and system of the same
EP2674449A1 (en) * 2012-06-11 2013-12-18 3M Innovative Properties Company Nanosilica coating assembly with enhanced durability
AU2013209338B2 (en) * 2012-08-17 2014-09-25 Rohm And Haas Company Substrate marking system
CN102998723B (en) * 2012-11-29 2016-03-16 法国圣戈班玻璃公司 Antireflection optical assembly and manufacture method
WO2014134594A1 (en) 2013-03-01 2014-09-04 Board Of Trustees Of The University Of Arkansas Antireflective coating for glass applications and method of forming same
CN105246986A (en) 2013-05-30 2016-01-13 3M创新有限公司 Poly(vinyl alcohol)-containing and silica nanoparticle multilayer coatings and methods
US10040953B2 (en) 2013-05-30 2018-08-07 3M Innovative Properties Company Poly(vinyl alcohol) and silica nanoparticle multilayer coatings and methods
US9925560B2 (en) 2013-05-30 2018-03-27 3M Innovative Properties Company Crosslinked poly(vinyl alcohol) and silica nanoparticle multilayer coatings and methods
CN105683302A (en) * 2013-10-04 2016-06-15 3M创新有限公司 Coatable composition, antistatic composition, antistatic articles, and methods of making the same
CN105322433B (en) * 2014-05-28 2020-02-04 深圳光峰科技股份有限公司 Wavelength conversion device and related light emitting device
WO2016011041A1 (en) * 2014-07-14 2016-01-21 Enki Technology, Inc. Coating materials and methods for enhanced reliability
US9376589B2 (en) 2014-07-14 2016-06-28 Enki Technology, Inc. High gain durable anti-reflective coating with oblate voids
US9382449B2 (en) 2014-09-19 2016-07-05 Enki Technology, Inc. Optical enhancing durable anti-reflective coating
US9598586B2 (en) 2014-07-14 2017-03-21 Enki Technology, Inc. Coating materials and methods for enhanced reliability
KR102293731B1 (en) 2014-10-16 2021-08-27 삼성디스플레이 주식회사 Window for display device and display device including the window
JP2016087561A (en) * 2014-11-06 2016-05-23 富士フイルム株式会社 Aqueous coating liquid, film, production method of the same, laminate and solar cell module
JP6892740B2 (en) * 2016-04-22 2021-06-23 パンサーフェス株式会社 Hydrophilicity-imparting agent, hydrophilic film forming method, hydrophilic film, and solar panel
US10814287B2 (en) 2016-05-13 2020-10-27 3M Innovative Properties Company Multilayer articles including coatings on microfiltration membrane substrates and methods of making same
DE102016225813A1 (en) * 2016-12-13 2018-06-14 Continental Automotive Gmbh Method for producing a transmittable three-dimensional motor vehicle interior element and motor vehicle interior element
WO2018169737A1 (en) 2017-03-15 2018-09-20 3M Innovative Properties Company Multilayer articles including coatings containing metal on microfiltration membrane substrates
GB201709562D0 (en) * 2017-06-15 2017-08-02 Grafmarine Power distrubution and cell storage apparatus
JP7307046B2 (en) * 2018-02-15 2023-07-11 国立大学法人大阪大学 Core-shell type semiconductor nanoparticles, method for producing the same, and light-emitting device
EP3808209B1 (en) * 2018-06-15 2023-11-29 Lg Chem, Ltd. Decoration member
US11584856B2 (en) 2018-06-20 2023-02-21 Saint-Gobain Performance Plastics Corporation Composite film with anti-reflective coating
KR102094192B1 (en) * 2018-09-07 2020-04-23 고려대학교 산학협력단 Anti-reflection coating film and manufacturing method thereof
JPWO2020067134A1 (en) * 2018-09-25 2021-09-02 日本電気硝子株式会社 Transparent goods
CN114902087A (en) * 2020-01-16 2022-08-12 3M创新有限公司 Composite cooling film comprising a reflective non-porous organic polymer layer and a UV protective layer
KR102668109B1 (en) * 2020-11-03 2024-05-22 한국전자통신연구원 Nano structure for controlling optical properties of optical device and manufacturing method thereof
WO2022113108A1 (en) * 2020-11-27 2022-06-02 International Advanced Research Centre For Powder Metallurgy And New Materials (Arci) Method of producing single layer omnidirectional broadband antireflective and super hydrophilic (antifogging) coatings for solar and other applications
US11912899B2 (en) 2021-03-24 2024-02-27 Sony Group Corporation Film, liquid paint and method
US11169306B1 (en) * 2021-04-08 2021-11-09 Mark Joseph Oneill Curvilinear prismatic film which eliminates glare and reduces front-surface reflections for solar panels and other surfaces
CN113113497B (en) * 2021-04-13 2023-01-24 河南大学 Solar cell using organic synergist and preparation method thereof
CN117546059A (en) * 2021-06-23 2024-02-09 3M创新有限公司 Optical film, backlight source and display
CN117567894B (en) * 2024-01-11 2024-04-05 中稀易涂科技发展有限公司 High-emission rare earth-based radiation refrigeration coating

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1189288A1 (en) * 2000-03-02 2002-03-20 Nippon Sheet Glass Co., Ltd. Photoelectric device
US20070074757A1 (en) * 2005-10-04 2007-04-05 Gurdian Industries Corp Method of making solar cell/module with porous silica antireflective coating
US20090246415A1 (en) * 2008-03-28 2009-10-01 Wataru Horie Functional film and display apparatus
WO2009120983A2 (en) * 2008-03-27 2009-10-01 Rensselaer Polytechnic Institute Ultra-low reflectance broadband omni-directional anti-reflection coating
WO2010084290A1 (en) * 2009-01-23 2010-07-29 Saint-Gobain Glass France Substrate en verre transparent glass substrate and method for producing such a substrate

Family Cites Families (48)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4082570A (en) * 1976-02-09 1978-04-04 Semicon, Inc. High intensity solar energy converter
US4229066A (en) 1978-09-20 1980-10-21 Optical Coating Laboratory, Inc. Visible transmitting and infrared reflecting filter
US5032461A (en) 1983-12-19 1991-07-16 Spectrum Control, Inc. Method of making a multi-layered article
US4842893A (en) 1983-12-19 1989-06-27 Spectrum Control, Inc. High speed process for coating substrates
US5097800A (en) 1983-12-19 1992-03-24 Spectrum Control, Inc. High speed apparatus for forming capacitors
US5125138A (en) 1983-12-19 1992-06-30 Spectrum Control, Inc. Miniaturized monolithic multi-layer capacitor and apparatus and method for making same
US5018048A (en) 1983-12-19 1991-05-21 Spectrum Control, Inc. Miniaturized monolithic multi-layer capacitor and apparatus and method for making
US4722515A (en) 1984-11-06 1988-02-02 Spectrum Control, Inc. Atomizing device for vaporization
EP0242460A1 (en) 1985-01-18 1987-10-28 SPECTRUM CONTROL, INC. (a Pennsylvania corporation) Monomer atomizer for vaporization
US4954371A (en) 1986-06-23 1990-09-04 Spectrum Control, Inc. Flash evaporation of monomer fluids
US5445871A (en) * 1990-10-30 1995-08-29 Kansai Paint Co., Ltd. Surface-modified plastic plate
MY109261A (en) 1991-09-27 1996-12-31 Kerr Mc Gee Chem Corp Attenuation of polymer substrate degradation due to ultraviolet radiation.
US5233465A (en) 1992-05-27 1993-08-03 The Dow Chemical Company Visibly transparent infrared reflecting film with color masking
EP0632507A3 (en) 1993-05-12 1995-11-22 Optical Coating Laboratory Inc UV/IR reflecting solar cell cover.
JPH06350114A (en) * 1993-06-08 1994-12-22 Souzou Kagaku:Kk Solar battery having texture structure where minute irregularity formed on surface by ultrasonic processing
JP2825736B2 (en) 1993-07-30 1998-11-18 京セラ株式会社 Dielectric ceramic composition and package for housing semiconductor element
GB9316437D0 (en) 1993-08-06 1993-09-22 Harcros Chemicals Uk Limited Zinc oxide and a process for making it
US5440446A (en) 1993-10-04 1995-08-08 Catalina Coatings, Inc. Acrylate coating material
SK283289B6 (en) 1993-10-04 2003-05-02 Presstek, Inc. (A Delaware Corporation) Cross-linked acrylate coating material useful for forming capacitor dielectrics and oxygen barriers
US6498683B2 (en) 1999-11-22 2002-12-24 3M Innovative Properties Company Multilayer optical bodies
JP3386906B2 (en) * 1994-01-18 2003-03-17 大日本印刷株式会社 Coating composition, manufacturing method thereof, coating film forming method and coating film
US5464667A (en) 1994-08-16 1995-11-07 Minnesota Mining And Manufacturing Company Jet plasma process and apparatus
US6083628A (en) 1994-11-04 2000-07-04 Sigma Laboratories Of Arizona, Inc. Hybrid polymer film
JPH10133002A (en) * 1996-10-30 1998-05-22 Canon Inc Antireflection film, production of this antireflection film and display device using this antireflection film
US6203898B1 (en) 1997-08-29 2001-03-20 3M Innovatave Properties Company Article comprising a substrate having a silicone coating
US6045864A (en) 1997-12-01 2000-04-04 3M Innovative Properties Company Vapor coating method
US6808658B2 (en) 1998-01-13 2004-10-26 3M Innovative Properties Company Method for making texture multilayer optical films
US6049419A (en) 1998-01-13 2000-04-11 3M Innovative Properties Co Multilayer infrared reflecting optical body
US6610766B1 (en) * 1998-03-12 2003-08-26 Kureha Kagaku Kogyo K.K. Polyvinylidene fluoride resin composition
DE69937764T2 (en) * 1998-09-22 2008-11-27 Fujifilm Corp. Process for the preparation of an anti-reflection film
EP1127381B1 (en) 1998-11-02 2015-09-23 3M Innovative Properties Company Transparent conductive oxides for plastic flat panel displays
JP2001057439A (en) * 1999-06-11 2001-02-27 Kanegafuchi Chem Ind Co Ltd Solar battery module
US6449093B2 (en) 1999-10-12 2002-09-10 3M Innovative Properties Company Optical bodies made with a birefringent polymer
JP2002365403A (en) * 2001-06-11 2002-12-18 Nippon Sheet Glass Co Ltd Low reflective film and transparent laminated body using the same
US7215473B2 (en) 2002-08-17 2007-05-08 3M Innovative Properties Company Enhanced heat mirror films
US7015640B2 (en) 2002-09-11 2006-03-21 General Electric Company Diffusion barrier coatings having graded compositions and devices incorporating the same
US7018713B2 (en) 2003-04-02 2006-03-28 3M Innovative Properties Company Flexible high-temperature ultrabarrier
US7019905B2 (en) 2003-12-30 2006-03-28 3M Innovative Properties Company Multilayer reflector with suppression of high order reflections
US7345137B2 (en) 2004-10-18 2008-03-18 3M Innovative Properties Company Modified copolyesters and optical films including modified copolyesters
US20070020451A1 (en) 2005-07-20 2007-01-25 3M Innovative Properties Company Moisture barrier coatings
US20070227579A1 (en) * 2006-03-30 2007-10-04 Benyamin Buller Assemblies of cylindrical solar units with internal spacing
US8018568B2 (en) * 2006-10-12 2011-09-13 Cambrios Technologies Corporation Nanowire-based transparent conductors and applications thereof
US8241713B2 (en) 2007-02-21 2012-08-14 3M Innovative Properties Company Moisture barrier coatings for organic light emitting diode devices
US20090062944A1 (en) 2007-09-04 2009-03-05 Apple Inc. Modifying media files
DE102008033910A1 (en) * 2008-03-06 2009-09-24 Johnson Controls Gmbh Optical arrangement i.e. multi-color beam combiner for head-up display of motor vehicle, has set of light sources and microprism-array, where set of light beams of light sources is aligned parallel to each other and/or superimposed
US20100035039A1 (en) 2008-08-07 2010-02-11 3M Innovative Properties Company Acicular silica coating for enhanced hydrophilicity/transmittivity
US8216357B2 (en) * 2009-09-25 2012-07-10 General Electric Company Protective coating compositions and devices
WO2011140273A2 (en) * 2010-05-04 2011-11-10 Sionyx, Inc. Photovoltaic devices and associated methods

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1189288A1 (en) * 2000-03-02 2002-03-20 Nippon Sheet Glass Co., Ltd. Photoelectric device
US20070074757A1 (en) * 2005-10-04 2007-04-05 Gurdian Industries Corp Method of making solar cell/module with porous silica antireflective coating
WO2009120983A2 (en) * 2008-03-27 2009-10-01 Rensselaer Polytechnic Institute Ultra-low reflectance broadband omni-directional anti-reflection coating
US20090246415A1 (en) * 2008-03-28 2009-10-01 Wataru Horie Functional film and display apparatus
WO2010084290A1 (en) * 2009-01-23 2010-07-29 Saint-Gobain Glass France Substrate en verre transparent glass substrate and method for producing such a substrate

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106132519A (en) * 2014-04-11 2016-11-16 3M创新有限公司 Microporous article of interconnection Nano particles of silicon dioxide three-dimensional porous network with acid sintering and preparation method thereof
CN106132519B (en) * 2014-04-11 2020-05-15 3M创新有限公司 Microporous article with acid-sintered interconnected silica nanoparticle three-dimensional porous network and method of making same
WO2017107783A1 (en) * 2015-12-25 2017-06-29 中国科学院上海高等研究院 Self-cleaning reflection reduction film and method of preparing same
CN107170852A (en) * 2017-06-27 2017-09-15 深圳市上古光电有限公司 A kind of light-weight solar component and its manufacture method

Also Published As

Publication number Publication date
US20210257504A1 (en) 2021-08-19
JP5869581B2 (en) 2016-02-24
KR102115937B1 (en) 2020-05-27
JP2013544670A (en) 2013-12-19
BR112013008304A2 (en) 2016-06-14
KR20130139959A (en) 2013-12-23
KR20170137206A (en) 2017-12-12
US20130186466A1 (en) 2013-07-25
CN103154320B (en) 2015-12-16
WO2012047422A1 (en) 2012-04-12
EP2625313A1 (en) 2013-08-14
EP2625313B1 (en) 2020-12-09
KR20190120456A (en) 2019-10-23
US20200123568A1 (en) 2020-04-23

Similar Documents

Publication Publication Date Title
CN103154320B (en) There is the antireflective article of the silica-based coating of nanometer titanium dioxide
CN103154319B (en) There is coating based on nano silicon and the antireflective article on barrier layer
US10514482B2 (en) Multi-layer optical films
TWI518156B (en) Anti-reflection and anti-glare coating composition, anti-reflection and anti-glare film, and method for preparation of the same
CN103270433B (en) Scribble the hyaloid polymeric antireflective film of nano SiO 2 particle, preparation method and use the light absorbing device of this film
US20130040073A1 (en) Silicone-based material
CN103261812A (en) Glass-like polymeric antireflective films, methods of making and light absorbing devices using same
TWI480099B (en) Photocatalyst coating body

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20151216

Termination date: 20210831